Concentrated liquid compositions of urease inhibitors for nitrogen sources

ABSTRACT

The present invention relates to increasing and/or maintaining nitrogen content in soil by administration of nitrogen sources particles coated with urease inhibitors. In one embodiment, urease inhibitors are dispersed in an improved organo liquid delivery system at concentration levels of 60-95%. In another embodiment, urease inhibitors were applied in a non-aqueous, organo liquid delivery system coating nitrogen sources particles utilizing simple blending equipment at temperatures of 20°-70° C. Another embodiment discloses dry, flowable nitrogen sources coated with a urease inhibitor which can be administered directly to the soil, to a dry natural and/or a manmade fertilizer or to a liquid fertilizer which provides for the reduction of nitrogen loss from the soil. In another embodiment, a composition of urea and &lt;0.2% dimethyl sulfoxide improves the crush resistance of the urea particles.

FIELD OF THE INVENTION

The present invention relates to increasing and/or maintaining nitrogencontent in soil by administration of granular or powdered nitrificationinhibitors coated with urease inhibitors. In one embodiment, ureaseinhibitors are dispersed in an improved organo liquid delivery system atconcentration levels of 50-90%. In another embodiment, urease inhibitorswere applied in a non-aqueous, organo liquid delivery system coatingsolid nitrification inhibitors utilizing simple blending equipment attemperatures of 20°-70° C. Another embodiment discloses a dry, flowableadditive containing a nitrification inhibitor coated with a ureaseinhibitor which can be administered directly to the soil, to a drynatural and/or a manmade fertilizer or to a liquid fertilizer whichprovides for the reduction of nitrogen loss from the soil due tomicrobial activity.

The present invention further relates to increasing and/or maintainingnitrogen content in soil by administration of improved stable liquidsolutions. In one embodiment, the stable liquid solutions comprise(aminomethylene) phosphinic acids and their salts as a urease inhibitordissolved in a Non-aqueous Organo Solvent Delivery System (NOSDS). Inanother embodiment, the stable liquid solutions comprises nitrificationinhibitors and (aminomethylene) phosphinic acids and their salts thatare co-dissolved in a NOSDS or blending solutions of each that has beendissolved in a NOSDS. In another embodiment, the stable liquid solutionscomprises urease inhibitors and (aminomethylene) phosphinic acids andtheir salts that are co-dissolved in a NOSDS or blending solutions ofeach that has been dissolved in a NOSDS. In another embodiment, thestable liquid solutions comprises Organo PolycarboxylateFunctionalities, (OPCF), and their salts and (aminomethylene) phosphinicacids and their salts that are co-dissolved in a NOSDS or blendingsolutions of each that has been dissolved in a NOSDS. In anotherembodiment, the stable liquid solutions comprises nitrificationinhibitors, urease inhibitors, Organo Polycarboxylate Functionalities,(OPCF), and their salts and (aminomethylene) phosphinic acids and theirsalts that are co-dissolved in a non-aqueous organo liquid deliverysystem (NOSDS) or blending solutions of each that has been dissolved ina NOSDS. In an embodiment, the stable liquid solutions are designed tobe used in conjunction with a nitrogen source or for direct applicationto the soil to slow or retard the loss of nitrogen in the soil.

In one embodiment, compositions are comprised of a) one or more ureaseinhibitors and b) a non-aqueous organo liquid delivery system (NOSDS),wherein the one or more urease inhibitors comprise between about 60-95%,by weight, of said compositions. In another embodiment, the one or moreurease inhibitors are dissolved in a non-aqueous organo solvent and thendelivered as a coating to the surfaces of nitrogen sources particlesutilizing simple equipment. In a variation, the compositions can beapplied to the surfaces of nitrogen sources through simple equipmentsuch as spray, meter and controlled flow applicators, wherein thenitrogen sources are at temperatures of between about 25° to 100° C.,30° to 100° C., 40° to 100° C., 50° to 100° C., 60° to 100° C., 70° to100° C., 80° to 100° C., 90° to 100° C., 25° to 90° C., 25° to 80° C.,25° to 70° C., 25° to 60° C., 25° to 50° C., 25° to 40° C., 25° to 35°C., 40° to 70° C., 50° to 80° C., and 0° to 100° C.

In another embodiment, discloses dry, flowable nitrogen sourcesparticles coated with urease inhibitors which can be administereddirectly to plant growth mediums, blended with dry natural and/ormanmade fertilizers or added to a liquid fertilizer, wherein theapplication results in imparting urease inhibition properties for thereduction of nitrogen loss in plant growth mediums due to ureaseactivities. In an embodiment, compositional levels as high as about 10%of urease inhibitors can be delivered to the surfaces of nitrogensources allowing for blending with other untreated nitrogen sourcesimparting urease inhibition to plant growth mediums. In a variation,application of a composition onto the surfaces of nitrogen sourcesparticles can be accomplished with lower levels of organo liquids. Inanother variation, high levels of urease inhibitors can be applied tothe surface of nitrogen sources' surfaces without adding high levels oforgano-solvents.

In another embodiment, high levels of non-aqueous organo liquid solventsystems with good solubilizing properties for nitrogen sources cannegatively impact the physical properties of the nitrogen sourcesparticles.

In an embodiment, the present invention relates to increasing andmaintaining nitrogen content in plant growth mediums by administrationof nitrogen sources coated with a composition comprised of i) one ormore urease inhibitors selected from the group consisting of (1)phosphoramides, (2) phosphinic acid organo amines and their salts, and(3) a non-aqueous organo solvent delivery system (NOSDS). In anotherembodiment, the urease inhibitor coated nitrogen sources can furthercomprise nitrification inhibitors, organo polycarboxylatefunctionalities and their salts, bio-actives and biologics. In anembodiment, compositions are designed to be used in conjunction with anitrogen source or for direct application to the plant growth mediums toretard the loss of nitrogen in the plant growth mediums throughinhibiting the urease enzymes' conversion of urea to ammonia.

BACKGROUND OF THE INVENTION

Nitrogen is an essential plant nutrient and is thought to be importantfor adequate and strong foliage. Urea provides large nitrogen contentand is the dominant nitrogen fertilizer. In the presence of soilmoisture, natural or synthetic ureas are converted to ammonium ion,which is then available for plant uptake. Ammonium can be furtherconverted by bacteria in soil to nitrate through a nitrificationprocess. Nitrate is also available for plant uptake. However, the ureausage efficiency is low. In one study used data from over 800experiments, it is estimated that only 51% of the N applied wasrecovered by cereals plant (Dobermann and Cassman 2005). In anotherliterature reference, it was reported that average urea efficiency incereals in China was 30-35% (Fan 2004).

There are two routes for urea loss. One is ammonia ventilation. Inpractice, nitrogen fertilizer is often just applied once at thebeginning of the growing season. The excessive ammonia from ureadegradation by urease in the soil bacteria may be leached toenvironment, especially water or converted to ammonia gas, which iscalled ammonia ventilation. Soil property, including titratable acidity,pH-H2O, urease activity and cation-exchange capacity, contributes about90% of ammonia ventilation (Watson CJ 1994). The other route isnitrification wherein ammonia is converted to nitrate by bacteria in thesoil, which is called nitrification. Excessive nitrate can be convertedinto nitric oxide or nitrous oxide by certain types of bacteria in thesoil, which is called denitrification.

Low efficiency of nitrogen fertilizer not only increases the cost offertilization, but also contributes significantly to environmentpollution. Ammonia has an obnoxious smell even at very low level andammonium in the water is toxic to water creatures (US EPA822-R-13-001).Nitrous oxide is a potent greenhouse gas, whose potency on globalwarming is 300 times stronger than carbon dioxide(http://epa.gov/climatechange/ghgemissions/gases/n2o.html). So,increasing the efficiency of urea fertilizer will both save the moneyand protect the environment, which is very desirable. To improve thelongevity of nitrogen nutrients in the soil, fertilizers have beentreated with nitrification inhibitors and urease inhibitors. Theseinhibitors can be deposited onto the surface of fertilizer granules as acoating or added to liquid fertilizers which are aqueous solution ofsuch nitrogen rich components as urea and ammonium nitrate (UAN).

UAN products are of particular interest since the nitrate portion ismobile in the soil and can move to roots for rapid nutrient uptake andthe ammonium portion can complex with clay particles and be released asa nitrogen nutrient over time while the urea portion is dependent uponbiological processes to degrade it into nitrogen compounds that are in aform that is absorbable by plants. The major advantage of such acompounded fertilizer is that it can provide quickly plant absorbablenitrogen nutrients and is also designed to provide nitrogen nutrientsover time. They are marketed as UAN followed by a number indicating the% nitrogen contained in the formulation such as UAN 28 or UAN 32 withthe number 28 and 32 denoting the nitrogen content.

However, UAN solutions also present challenges to economically maintainsuitable levels of nitrogen nutrients over time during warmth of thegrowing season due to the high microbial populations in the soil fuelingthe decomposition of urea to ammonia and the oxidation of ammonia tonitrates and NO_(x) at a rapid rate. Thus, finding economical deliveryformulations that are safe for the environment and for animals and thatcontain the proper balance of nitrification inhibitors and ureaseinhibitors that may be applied directly to liquid fertilizers such asUAN would be advantageous to the agricultural industry. Such a treatedliquid fertilizer would also assist in slowing two major biologicalprocesses that cause substantial loss of nitrogen in soil whilesimultaneously assisting in controlling pollution of our water andatmosphere. Some products on the market can achieve the goal, such asNeon series from EcoAgro Resources, in which NBPT and DCD are dissolvedin organic solvents. However, such formulations are not the mosteconomical way to achieve the delivery of urease and nitrificationinhibitors to liquid fertilizers due to the high cost of the organicsolvent, which is not necessary for UAN products, and the lowercomposition percentages of the inhibitors in the liquid formulationswhich necessitate a larger percentage application of these liquiddispersed systems.

Herein, is described an innovation in which the nitrification inhibitorcrystals or powder is coated with a high concentration of ureaseinhibitor dissolved in an organic solvent. These urease inhibitor coatednitrification solids are ready to quickly dissolve in the UAN resultingin a clear and stable solution making it easy to insure a homogeneoussolution for an even application of urease and nitrification inhibitorsto the soil. Compared to its liquid equivalents, the current technologyis inexpensive to make, transport and store, while delivering a higherconcentration of inhibitors per weight unit of product.

Agriculture currently utilizes fertilizers to deliver the needednutrients of nitrogen, phosphorus, potassium, sulfur, calcium, andmagnesium to plants through the application of fertilizers to the soil.Nitrogen generally is the most yield-limiting and costly nutrientelement in crop production. Fertilizers are based on nitrogen content,mainly urea and additional plant nutrients and additives. Fertilizerscan either be formulated as man-made products or natural organic basedanimal manure. Nitrogen is the primary nutrient in fertilizers and ureais the primary nitrogen source in fertilizers. Thus, fertilizers havebecome one vehicle for increasing the nitrogen content in the soil toassist in maintaining the health, overall quality, growth and yields ofmany of the plants important to agriculture and to civilization.Nitrogen is usually formulated into fertilizer by one or more of ureaand/or ammonium nitrate and/or ammonium sulfate and/or manure and/orammonium phosphate, anhydrous ammonia and/or the like.

Generally, the fertilizer is applied to the soil as either a liquid, asolid or sub-soil as a gas. Maintaining a sufficient level of nitrogenconcentration in the soil proves difficult over time due to nitrogen andnitrogen containing compounds (such as urea) solubilities in water.

When rain or water run-off contacts the soil, the nitrogen or nitrogencontaining compounds may be carried with the water to surroundingwater-ways.

Alternatively, the degradation of nitrogen content may be attributed tovolatilization (such as for ammonia and NOx where x is 1, 2 or 3) andwater runoff due to the better water solubility of nitrites/nitrates.Loss due to volatilization is sometimes driven by a urease enzyme thatcatalyzes hydrolysis of urea to ammonia and carbon dioxide and to thebiological oxidation by soil microbes, such as Nitrosomonas bacteria, ofNH₃ or NH₄ to NOx's such as nitric oxide, an atmospheric greenhouse gaswhich, on a molecular basis, has 310 times the global warming potentialof carbon dioxide. This results in a substantial loss of nitrogencontent in the fertilizer impacting costs to the farmer. Moreover, theloss of nitrogen from the soil results not only in water pollution butalso atmospheric pollution.

Nitrogen in the soil is also lost by the attack of nitrogen and nitrogencontaining compounds (such as urea) by enzymes like the urease enzyme.Attack by the urease enzyme causes urea to degrade to carbon dioxide andammonia. Biological oxidations by soil microbes, such as Nitrosomonasbacteria, of ammoniacal nitrogen to nitrate nitrogen are also a cause ofthe diminishing nitrogen content in soil over time. While the conversionof urea to ammonia and oxidation of ammonia to nitrates within the soilis beneficial to plants, conversions occurring on top of the soil, wherefertilizers are applied, also results in a loss of nitrogen. To improvethe longevity of nitrogen in the soil, fertilizers have been treatedwith nitrification inhibitors and urease inhibitors. These inhibitorsare usually coated onto the surface of fertilizer granules, added toaqueous liquid fertilizers, added to molten nitrogen sources previous tothe formation of a solid particle or introduced to a liquefied gas forsub-surface injection into soil.

Thus, it is desired that one increase the life expectancy of nitrogen inthe soil to insure more consistent levels of nitrogen during the growingseason while also decreasing the number of times the fertilizer isapplied to the soil. Increasing the life expectancy of nitrogen in soilwhile simultaneously decreasing the number of applications of fertilizerwill lower the overall cost to the agriculture industry while at thesame time limiting the amount of nitrogen carried into the waterways.Untreated nitrogen sources that are used create polluting conditionsthat are believed to have fueled the formation of the Gulf Dead Zone,the formation of toxic algal blooms as well as damage to drinking watersupplies. Thus, finding delivery formulations that are safe for theenvironment and for animals and that contain the proper levels ofnitrification inhibitors and/or urease inhibitors that may be applieddirectly to the soil in a liquid form or imparted onto fertilizergranules as a one-step application would be advantageous to theagricultural industry. Such a treated fertilizer would also assist inslowing two major biological processes that cause substantial loss ofnitrogen in soil while simultaneously assisting in controlling pollutionof our water and atmosphere.

It is also desired to utilize stable liquid solutions that have improvedpH, hydrolytic and thermal stability and create lower odor resulting inimprovements flexibility in application to a nitrogen source.

While many techniques and inventions have a positive impact ofmaintaining the level of nitrogen in the soil, they also havesignificant problems. For example, problems that have adversely affectthe agricultural industry include costs of improvement, loss ofviability upon storage, the inability to deliver consistent levels offertilizer due to poor coating of the inhibitors or clumping of granulesand the aqueous, low pH and thermal instability of alkyl thiophosphorictriamide such as NBPT resulting in a foul odor and loss of efficacy.Thus, there is a need for a composition, which addresses theseshortcomings.

Agriculture currently utilizes fertilizers to deliver the needednutrients of nitrogen, phosphorus, potassium, sulfur, calcium, andmagnesium to plants through the application of fertilizers to the plantgrowth mediums. Nitrogen generally is the most yield-limiting and costlynutrient element in crop production. Fertilizers are based on nitrogencontent, mainly urea and additional plant nutrients and additives.Fertilizers can either be formulated as man-made products or naturalorganic based animal manure. Nitrogen is the primary nutrient infertilizers and urea is the primary nitrogen source in fertilizers.Thus, fertilizers have become one vehicle for increasing the nitrogencontent in the plant growth mediums to assist in maintaining the health,overall quality, growth and yields of many of the plants important toagriculture and to civilization. Nitrogen is usually formulated intofertilizer by one or more nitrogen sources selected from the groupconsisting of urea, ammonium nitrate, ammonium sulfate, manure,diammonium phosphate, monoammonium phosphate, dicyandiamide, andcompost.

Urea provides a large nitrogen content and is one of the best of allnitrogenous fertilizer materials, which consequently makes it anefficient fertilizer compound. In the presence of plant growth mediums'moisture, natural and/or synthetic ureas are converted to ammonium ion,which is then available for plant uptake. When applied as a fertilizer,native bacteria enzymatically convert urea to two molar equivalents ofammonium ion for each mole of urea as demonstrated by the following tworeactions:

CO(NH₂)₂+2H₂O→(NH₄)₂CO₃

(NH₄)₂CO₃+2H⁺→2NH₄ ⁺+CO₂+H₂O

In the presence of water, the ammonium thus produced is in equilibriumwith ammonia. The equilibrium between NH₄ ⁺ and NH₃ is pH dependent, inaccordance with the following equilibrium:

NH₄ ⁺+OH⁻↔NH_(3(solution))+H₂O

As such, gaseous ammonia losses are higher at higher pH values. The fluxof NH3 from soil is primarily dependent on the NH₃ concentration, pH,and temperature. In the presence of oxygen, ammonium can also beconverted to nitrate (NO₃ ⁻). Nitrogen in both its ammonium and nitrateforms may then be taken up as nutrient substances by growing plants.

The ammonium ion can also ultimately be converted to ammonia gas, whichescapes to the air. The concentrations of NH3 in the air and in solutionare governed by Henry's law constant (H), which is a function oftemperature:

└NH_(3(air))┘=H└NH_(3(solution))┘

Urea fertilizer is often just applied once at the beginning of thegrowing season. A weakness in this nitrogen delivery system involves thedifferent rates at which ammonium ions are produced in the soil, and therate at which ammonium ions are required by the plant during its growingseason. The generation of ammonium ions from the breakdown of urea isfast relative to its uptake by plants, allowing a considerable amount ofthe fertilizer nitrogen to go unutilized or to be lost to the atmosphereas ammonia gas, where it is no longer available to the plant. In onestudy used data from over 800 experiments, it is estimated that only 51%of the N applied was recovered by cereals plant (Dobermann and Cassman2005). In another literature reference, it was reported that averageurea efficiency in cereals in China was 30-35% (Fan 2004). Thus, thereis a desire to control the hydrolysis of urea to ammonium and ammoniagas, thereby making the urea fertilizer more effective for plant growth.

Nitrogen sources particles' coating technologies utilizes solutionscontaining urease inhibitors to coat nitrogen sources in order to impartlongevity of plant available nitrogen in plant growth mediums. However,these technologies have limitations when the application level of thesolutions containing urease inhibitors approaches 0.75% of the weight ofthe nitrogen sources. Higher % coating levels causes the nitrogensources to become wet negatively impacting the coated nitrogen sourcesprocessability in mixing and application equipment with the formation ofclogs and high level of deposition on equipment parts.

These issues increases the cost of fertilizing by requiring morefrequent cleaning of equipment and the formation of clumps of fertilizerimpacting evenness of fertilizer application to the plant sourcemediums. In an embodiment, solutions containing urease inhibitors thatare formulated around solvent systems with strong nitrogen sourcessolubilizing properties can negatively impact the physical properties ofthe nitrogen sources particles. In a variation, the crush strength ofthe nitrogen sources particles is negatively impacted, wherein saidsolutions' compositions contain large percentages of strong nitrogensource solubilizing solvents. Thus, compositions that

-   -   1. are safe for the environment,    -   2. safe for animals,    -   3. contain high levels urease inhibitors,    -   4. contain low levels of organo solvents,    -   5. have minimum impact of nitrogen sources particles' physical        properties    -   6. can be applied directly to the plant growth mediums in a        liquid form or coated onto fertilizer granules surfaces        would be advantageous to the agricultural industry.

DESCRIPTION OF THE PRIOR ART

Of particular interest is increasing the length of time that nitrogennutrients are available to plants from an aqueous urea/ammonium nitratebased liquid fertilizer (referred to herein as UAN). When applied tosoil, the urea component of the UAN hydrolyzes to ammonia through theaction of urease enzymes generated by numerous fungi and bacteriapresent in the soil while the ammonia generated by the urease action onurea and present in the ammonium nitrate can be oxidized to nitrates.While these conversion processes are necessary to create nitrogennutrients in a plant available form, they occur at a rate too rapid tobe absorbed by plants leading to the quick depletion of these nutrientseither through volatilization or water runoff. The utilization of ureaseand nitrification inhibitors is required to slow both biologicalprocesses to extend the availability of nitrogen nutrients to plants.

Various methods as disclosed in the patents below, which areincorporated by reference in their entireties, have been proposed anddeveloped for controlling nitrogen nutrients loses from soil treatedwith an aqueous solution of urea and ammonium nitrate.

Michaud (U.S. Pat. No. 4,234,332) describes aqueous solutions ofcommonly used fertilizers which also contain dicyandiamide, in an amountto provide at least 10% by weight of dicyandiamide nitrogen which is aneffective nitrification inhibitor.

Sutton et al. (U.S. Pat. No. 5,024,689) teach the use of liquidfertilizer that includes urease inhibitors such as NBPT andnitrification inhibitor such as dicyandiamide (referred to herein asDCD) in aqueous mixtures of urea, ammonium polyphosphate, ammoniumthiosulfate and potentially other plant growth improving compounds. Thisapproach has drawbacks in that NBPT and DCD are not particular solublein water especially water containing high salt contents.

Weston, et al (U.S. Pat. No. 5,352,265) discloses a granular urea basedfertilizer in which NBPT in 25-50% of solvent selected from the groupconsisting of liquid amides, 2-pyrrolidone, and N-alkyl 2-pyrrolidonesis blended directly into molten urea prior to its granulation. DCD maybe added to the urea melt as a solid or in dissolved form along with theNBPT. This approach is equipment specific and is generally high in cost.

Omilinsky, et al (U.S. Pat. No. 5,698,003) Improved solvent systems forthe formulation of N-alkyl thiophosphoric triamide urease inhibitorscomprised of a solvent selected from the group consisting of glycols andglycol derivatives and optionally, the formulations can contain aco-solvent selected from the group consisting of liquid amides,2-pyrrolidone and N-alkyl 2-pyrrolidones, and/or a nonionic surfactant.These solutions are to be applied onto solid urea containing fertilizersor added to liquid urea containing fertilizer formulations.

McKnight (U.S. Pat Application Publication No 20140090432) discloses asolvent delivery system for the urease inhibitor that can be utilized asa coating or an additive to a liquid fertilizer. McKnight (U.S. PatApplication Publication No 20150143860, 20150299062 and 20150315092)illustrate solvent delivery systems for urease and nitrificationinhibitors for coating granular fertilizers or for adding to liquidfertilizers.

Ortiz-Suarez (U.S. Pat. No. 9,266,789) teaches of solvent deliverysystems for Dicyandiamide, a nitrification inhibitor, to be utilizedwith UAN solutions or coated onto the surface of urea for increasing thelife of plant available nitrogen nutrients.

While Omilinsky, McKnight and Ortiz-Suarez utilize organo solvents todissolve the inhibitors, the utility of these types of technologies arenot cost effective because the organo solvents are an added cost as theynot necessary for aqueous fertilizers and the % inhibitors are too lowfor aqueous fertilizers thus requiring higher percent usage to meetinhibition requirements.

Sutton (U.S. Pat. No. 8,562,711, U.S. Pat Application Publication No2007157689 and 20130283873) provides a method for developing a dry,flowable additive for aqueous urea-based fertilizers based on solid ureaformaldehyde polymer (referred to herein as UFP) coated with N-(n-butyl)thiophosphoric triamides either molten or in a solvent system as adispersion or suspension for inhibition of urease enzyme and,optionally, dicyandiamide that imparts nitrification inhibition toreduce nitrogen loss from the soil. Also, Sutton provides that the dryadditive may be blended with molten or solid urea to form a solidurea-based fertilizer with reduced nitrogen loss from the soil. Thisapproach requires the pre coating of UFP granules with a solvent basedNBPT and then blended with dry DCD which adds more cost to the finalproduct. UFP's have poor solubility in water and especially in watercontaining high levels of salt. This lack of solubility requires thatthe UFP undergoes special process to insure that it's particle size besmall enough to be suspended in an aqueous solution making thehomogeneity of the application of the inhibitor package more difficultas the NBPT resides on the insoluble UFP particle. The resulting aqueousfertilizer containing a product of this technology is milky inappearance making it difficult to determine when a product of thistechnology has completely dissolved and the coated UFP settles out uponstanding impacting the homogeneity of the resulting aqueous fertilizerresulting in uneven application of the inhibitors to the soil.

While many of these techniques have a positive impact of maintaining thelevel of nitrogen in the soil, they also have significant problems.Thus, there is a need for a composition, that is easy to dissolveresulting in a clear, stable solution in order to insure homogeneity ofthe inhibitors throughout the aqueous fertilizer and which can deliverthe required levels of urease and nitrification inhibitors in aneconomically and homogeneous manner to plants and to the soil.

Various methods as disclosed in the patents below, which areincorporated by reference in their entireties, have been proposed anddeveloped for controlling volatile nitrogen loses from urea.

Weston et al. (U.S. Pat. No. 5,352,265) discloses a granular urea basedfertilizer in which N(n-butyl) thiophosphoric triamide (NBPT) in 25-50%of solvent selected from the group consisting of liquid amides,2-pyrrolidone, and N-alkyl 2-pyrrolidones is blended directly intomolten urea prior to its granulation. DCD may be added to the urea meltas a solid or in dissolved form along with the NBPT. This approach isequipment specific and is generally high in cost and exposes thethermally unstable NBPT to temperatures ≥120° C.

Urease inhibiting materials other than NBPT have been disclosed. Someexamples include the use of polysulfide and thiosulfate salts as taughtby Hojjatie et al (US Patnet Application Publication No. 2006/0185411A1).

Kolc at al. (U.S. Pat. No. 4,530,714) teach the use of aliphaticphosphoric triamide urease inhibitors, including the use of NBPT forthis purpose. Kolc reveals the use of aqueous and organic carriermediums, but specifies volatile (and flammable) solvents from the groupincluding acetone, diisobutylketone, methanol, ethanol, diethyl ether,toluene, methyl chloride, chlorobenzene, and petroleum distillates. Theprinciple reason for the use of these solvents was to assure thatnegligible amounts of solvent residue be retained on the crop. Kolc alsoteaches effective levels of urease inhibition in a plant growth mediumwith at least 0.02 parts by weight of a phosphoric triamide applied to1,000,000 parts by weight of plant growth medium or stated differently aplant growth medium with 0.02 ppm of a phosphoric triamide should haveeffective urease inhibition. Kolc states effective levels of phosphorictriamide in plant growth mediums would be 0.02-5000 ppm, 1-1000 ppm and5-100 ppm would provide effective urease inhibition.

Gabrielson (U.S. patent application Ser. No. 15/552,675—U.S. PatentApplication Publication No. 20180044254) teaches the utilization of theaddition of a liquid concentrate of up to 95% N-(n-butyl) thiophosphorictriamide (NBPT) in N-Methyl-2-pyrrolidone (NMP) to molten urea attemperatures of 115-120° C. before prilling or granulation of the ureato ensure homogeneous distribution of NBPT throughout the urea particle.He also demonstrates that higher purity NBPT has better storagestability versus lower purity NBPT due to the slower degradation of highpurity NBPT. He also demonstrates how temperatures of 22° C. versus 45°C. impact the stability of NBPT. Gabrielson states that it is thepresence of impurities in the lower purity NBPT that promotes thefurther decomposition of the NBPT into non-effective substances during alonger storage and is the main cause of urease inhibitor degradationduring a long term storage. However, he does not show how temperaturesof 75-120° C. impacts the purity of the NBPT as this is the range oftemperatures that the NBPT is exposed to in the processes, wherein theconcentrated solutions containing NBPT are added to molten urea and thesubsequent formation of a urea particle. Gabrielson states that theconcentration of the urea is 94-99% with the removal of water and thatthe temperature of the urea must be maintained at 120° C. to keep itliquid (pure urea has a melt point of 132.7° C.). Exposing NBPT tomoisture and high temperatures results in the formation NBPT degradativespecies and, as shown by Gabrielson, the presence of these speciesnegatively impact the remaining NBPT which leads to poorer storagestability and further reduces the effectiveness of concentratedsolution's urease inhibition capabilities.

The industry needs a technology that are compositions of highlyconcentrated solution of urease inhibitors, wherein i) the ureaseinhibitors' weight percent is between about 60-95% of the composition ofthe solution, ii) are liquid at a temperature range of between about−20-70° C., iii) can be applied at medium temperatures as coating ofnitrogen sources particles at temperatures of 40-70° C. to ensure lowerthermal degradation of urease inhibitors such as NBPT, and iv) thecompositions comprise a non-aqueous organo liquid delivery system thatis safe for human contact and for the environment.

BRIEF SUMMARY OF THE INVENTION

Urea and ammonium nitrates are desirable starting materials forfertilizers and fertilizer additives, which can provide high nitrogencontent and can be used in fertilizer products that provide phosphorusor potassium as primary nutrients, and calcium, magnesium, or sulfur assecondary nutrients or micronutrients such as boron, copper, iron,manganese, molybdenum and zinc. These fertilizer products deliver thenutrients to the soil and through numerous biological processes can beconverted to forms that are capable of being absorbed by plants. The useof a nitrification inhibitor such as cyanoamides, typically,dicyandiamide (DCD) by itself or combined with a urease inhibitor suchas phosphoramides are one embodiment of the invention. In an embodiment,the present invention relates to an additive that imparts to liquid orsolid manmade fertilizer, manure, waste or compost an increasedlongevity of plant available nitrogen in the soil wherein the additiveis a dry, flowable composition produced by coating nitrificationinhibitor with a urease inhibitor dissolved in a Non-aqueous OrganicSolvent Delivery System (NOSDS) at concentrations of urease inhibitorsin the NOSDS of 50-90%. The resulting coated nitrification inhibitorbecomes an additive that can be mixed with granular, natural orsynthetic, fertilizer or added to aqueous fertilizer in particularcombination of urea and ammonium nitrate that have been dissolved inwater (commercial name of UAN). The inclusion of the combination ofnitrification and urease inhibitors which will inhibit biologicaloxidation of ammonia by soil microbes, such as Nitrosomonas bacteria andinhibit the enzymatic action of urease slowing the conversion ureanitrogen to ammoniacal nitrogen.

The present invention provides for a composition that is easy todissolve resulting in a clear, stable solution in order to insurehomogeneity of the inhibitors throughout the aqueous fertilizer andwhich can deliver the required levels of urease and nitrificationinhibitors in an economically and homogeneous manner to plants and tothe soil.

In an embodiment, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors dissolved in a Non-aqueous OrganoSolvent Delivery System (NOSDS). In a variation, the present inventionrelates to stable liquid solutions comprising (aminomethylene)phosphinic acids and their salts utilization as urease inhibitors incombination with nitrification inhibitors by either blending liquidsolutions containing each material or combining the two inhibitors byco-dissolving them together in a non-aqueous organo liquid deliverysystem (NOSDS).

In a variation, the present invention relates to stable liquid solutionscomprising (aminomethylene) phosphinic acids and their salts utilizationas urease inhibitors in combination with other urease inhibitors byeither blending liquid solutions containing each material or combiningthe two inhibitors by co-dissolving them together in a non-aqueousorgano liquid delivery system (NOSDS). In another variation, the presentinvention relates to stable liquid solutions comprising (aminomethylene)phosphinic acids and their salts utilization as urease inhibitors incombination with Organo Polycarboxylate Functionalities, (OPCF), andtheir salts by either blending two separate liquid solutions containingeach material or combining the by dissolving them together in annon-aqueous organo liquid delivery system (NOSDS) formulation. Inanother variation, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors in combination with nitrificationinhibitors, urease inhibitors and OPCFs and their salts by eitherblending liquid solutions containing each material or combining byco-dissolving them together in a NOSDS. The resulting stable liquidsolutions can then be applied to fertilizer or to just nitrogen sourcesto impart inhibiting the conversion of a nitrogen source to ammoniaand/or nitrate and free up soil bound phosphates and micronutrients.

In one embodiment, improved delivery formulations have been developedthat deliver expected and effective levels of (aminomethylene)phosphinic (AMP) acids and their salts that inhibits microbialconversion of nitrogen sources to ammonia increasing the nitrogenlongevity in the soil. In an embodiment, it has been found that thedelivery formulations of the present invention provide a liquid vehicleto deliver an even, non-clumping application of the desired inhibitorsto the fertilizer granule. In another embodiment, these AMP acids andtheir salts deliver urease inhibition in water containing nitrogensources such as urea ammonium nitrate solutions (UAN) and fresh animalmanure. Not to be bound by theory, the AMP inhibitors have betterhydrolytic thermal and low pH stability versus standard ureaseinhibitors such as alkyl thiophosphoramides such as N-(n-butyl)thiophosphoric triamide (NBPT) due to the methylene linkage between thephosphorous and the nitrogen. In another embodiment, AMP acids and theirsalts deliver urease inhibition to nitrogen sources produced by hightemperature processes by injecting the stable liquid solution comprisingAMP acids and their salts directly into the nitrogen source's moltenpool due to the AMP acids and their salts superior thermal stabilitywhen compared to N-(n-butyl) thiophosphoric triamide (NBPT). In avariation, the AMP acids and their salts do not generate a sulfur odorduring storage as a liquid formulation or as incorporated with anitrogen source.

In an embodiment, to improve the longevity of nitrogen in the soil, ithas been found that one can incorporate both a nitrification inhibitorand AMP acids and their salts with a fertilizer. In an embodiment, theimproved delivery systems of the present invention can be utilized as avehicle to impart one or more nitrification inhibitors such as, but notlimited to 2-chloro-6-(trichloromethyl)pyridine,4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazineCL-1580, Dicyandiamide (DCD), thiourea, 1-Mercapto-1,2,4-triazole,DCD/formaldehyde reaction products, methylene bis dicyandiamide and2-Amino-4-chloro-6-methylpyrimidine. The combined impact of using anitrification inhibitor together with AMP acids and their salts insolution in the NOSDS lowers the cost of fertilizer by utilizing aone-step application to granules and delivering optimized levels of bothinhibitors improving the longevity of nitrogen in the soil.

Thus, in one embodiment, the present invention relates to compositionscomprising NOSDS and AMP acids and their salts wherein the NOSDS:

-   -   Are environmentally safe;    -   Have flashpoints above 145° F.;    -   Are inherently rated safe for contact with humans and animals;    -   Maintain AMP acids and their salts at levels of 1-80% in        solution to storage temperatures down to at least 10° C.;    -   Provides improved even application to fertilizer granules of        urease inhibitors while not causing clumping of the granules.

Thus, in an embodiment, not to be bound by theory, the present inventionrelates to improved hydrolytic, low pH and thermal stabilities of theAMP acids and their salts, over alkyl thiophosphoramides in whichN-(n-butyl) thiophosphoric triamide (NBPT) is one particularly effectiveurease inhibitor. In one embodiment, because the NOSDS is effectivelynon-water containing, a combination of AMP acids and their salts andNBPT can be formulated utilizing two different urease inhibitors in onesolvent delivery system

In one embodiment, it has also been discovered that while variousorgano-liquids might meet some of the above criteria, the deliverysystem of the present invention can be optimized to provide aformulation with a high concentration of inhibitors while maintaining alow chill point by combining two or more organo-liquids in a solvatingsystem. In one embodiment, the NOSDS can also serve as the reactionmedium for the synthesis of the AMP acids and their salts.

In one embodiment, the present invention relates to an effective solventcombination that comprises dimethyl sulfoxide (DMSO), which can be usedin combination with another organo-liquid delivery system that has a lowchill point and good solvating properties. One advantage of using DMSOis that DMSO can be a source of the important nutrient of sulfur.

In an embodiment, the present invention relates to compositions thatimparts to one or more nitrogen sources selected from the groupconsisting of i) urea, ii) urea, formaldehyde reaction products, iii)urea, formaldehyde, and ammonia reaction products, iv) manure, v)dicyandiamide and vi) compost an increased longevity of plant availablenitrogen in the plant growth mediums. In an embodiment, the one or moretreated nitrogen sources are a dry, flowable composition produced bycoating one or more nitrogen sources with compositions comprised of a)one or more urease inhibitors and b) a non-aqueous organic solventdelivery system (NOSDS), wherein the one or more urease inhibitorscomprise between about 60-95%, 65-95%, 70-95%, 75-95%, 80-95%, 85-95%,60-80%, 65-80%, 70-80%, 75-80%, 60-70%, and 65-70% by weight of thecompositions. In a variation, the resulting coated nitrogen sourcesbecome a delivery system for imparting effective levels ureaseinhibitions at about at least 0.02 ppm to plant growth mediums. In anembodiment, the resulting coated nitrogen sources becomes a deliverysystem for imparting effective levels urease inhibitions at 0.02-5,000ppm, 1-1000 ppm, and 5-100 ppm to the plant growth mediums. The ureaseinhibitor coated nitrogen sources can be mixed with other granular,natural or synthetic fertilizers. In a variation, the urease inhibitorcoated nitrogen sources can be added to water to produce a liquid ureafertilizer, wherein the aqueous liquid fertilizer becomes a deliverysystem for imparting effective levels of urease inhibitions to the plantgrowth medium. The inclusion of urease inhibitors inhibits the enzymaticaction of urease on urea and UFP slowing the conversion of urea nitrogento ammoniacal nitrogen.

In an embodiment, the compositions comprise concentrations of ureaseinhibitors, wherein the concentration of urease inhibitors is within thepercent weight range of between about 60-95%, 65-95%, 70-95%, 75-95%,80-95%, 85-95%, 60-80%, 65-80%, 70-80%, 75-80%, 60-70%, and 65-70% ofthe compositions, and wherein these compositions are liquid and fluid attemperatures in the range of between about −20-70° C. In a variation,the compositions are topically applied to nitrogen sources, wherein thenitrogen sources are at temperatures of between about 20-70° C., 30-70°C., 40-70° C., 50-70° C., 60-70° C., 20-60° C., 30-60° C., 40-60° C.,50-60° C., 20-50° C., 30-50° C., 40-50° C., 20-40° C., and 30-40° C.,wherein the treated nitrogen sources composition comprise between about0.01-10%, 0.01-8%, 0.01-6%, 0.01-4%, 0.01-3%, 0.01-2%, 0.1-10%, 0.1-8%,0.1-6%, 0.1-4%, 0.1-2%, 0.1-1%, 0.1-0.75%, 0.1-0.5%, 0.1-0.25%,0.25-10%, 0.25-5%, 0.25-1%, 0.25-0.75%, 0.5-10%, 0.5-5%, 0.5-2%, 0.5-1%,0.5-0.75%, 1-10%, 2-10%, 3-10%, 4-10%, 5-10%, 6-10%, 1-5%, and 1-6% ofone or more urease inhibitors.

In an embodiment, the present invention comprises compositions thatimparts to one or more nitrogen sources selected from the groupconsisting of i) urea, ii) urea, formaldehyde reaction products, iii)urea, formaldehyde, and ammonia reaction products, iv) manure, v)dicyandiamide and vi) compost an increased longevity of plant availablenitrogen in the plant growth medium, wherein the composition is liquidand fluid at temperatures in the range of between about −20 to 70° C.,−20 to 50° C., −20 to 40° C., −20 to 30° C., −10 to 70° C., 0 to 70° C.,10 to 70° C., 20 to 70° C., 30 to 70° C., 40 to 70° C., 50 to 70° C., 60to 70° C., 20 to 60° C., 30 to 60° C., 40 to 60° C., 50 to 60° C., 20 to50° C., 30 to 50° C., 40 to 50° C., 20 to 40° C., and 30 to 40° C.,wherein the composition comprises a) one or more urease inhibitors andb) NOSDS, and wherein the urease inhibitors are in the percent weightranges of between about 60-95%, 65-95%, 70-95%, 75-95%, 80-95%, 85-95%,60-80%, 65-80%, 70-80%, 75-80%, 60-70%, and 65-70% of the compositions.

In an embodiment, the compositions comprise a NOSDS, wherein the NOSDScomprises one or more polar aprotic solvents. In a variation, the NOSDScomprises one or more solvent selected from the group consisting ofpolar aprotic, aprotic and protic solvents. In one embodiment, thedelivery formulations have been developed that deliver effective levelsof urease inhibitors as a coating on nitrogen sources particles thatincrease the plant available nitrogen longevity of particulatefertilizers when applied to plant growth mediums. In an embodiment, ithas been found that the delivery formulations of the present inventionprovide a liquid vehicle at temperature ranges of between about −20 to70° C., −20 to 50° C., −20 to 40° C., −20 to 30° C., −10 to 70° C., 0 to70° C., 10 to 70° C., 20 to 70° C., 30 to 70° C., 40 to 70° C., 50 to70° C., 60 to 70° C., 20 to 60° C., 30 to 60° C., 40 to 60° C., 50 to60° C., 20 to 50° C., 30 to 50° C., 40 to 50° C., 20 to 40° C., and 30to 40° C. for delivering an even, non-clumping application of effectiveurease inhibitors levels to nitrogen sources surfaces. In a variation,the high concentrations of urease inhibitors are delivered to thesurfaces of nitrogen sources particles with minimal NOSDS, wherein theimpact on the physical properties of the nitrogen sources particles isminimized by low levels of the NOSDS.

In an embodiment, these new liquid delivery compositions for coatingnitrogen sources are based on a non-aqueous organic solvent deliverysystem (NOSDS), which improves storage life of urease inhibitors such asalkyl thiophosphoric triamides over those formulations containinggreater than 1% water.

In an embodiment, the compositions can further comprise a colorant,wherein the colorant composition does not comprise water or alcohol. Ina variation, colorants are dissolved into the composition or into aNOSDS which is then added to the composition to enhance visualconformation of the evenness of the coating of nitrogen sources'surfaces.

In an embodiment, the compositions can further comprise one or moremembers selected from the group consisting of surfactants, buffers,fragrance/odor masking agents, micro-nutrients, and flow modifiers suchas silicas.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1: Nitrate nitrogen concentration for soil samples with varyinglevels of liquid containing nitrification inhibitor (lbs. per ton ofurea) for one to five weeks post urea application, with soil moistureadjusted weekly to 80% field capacity.

FIG. 2: 2M KCl extraction of soil for presence of NH₄—N and NO₃—N todetermine impact of rate of liquid containing nitrification inhibitoraddition. Data collected is the average of 8 weeks of soil extractions.

FIG. 3: Average of headspace analysis for NH₃ to determine impact ofrate of liquid containing urease inhibitor addition. Data was collectedover a 16 day period.

DETAILED DESCRIPTION

The following words are given the meanings ascribed below.

Fertilizer, in this invention, is defined as any material of natural orsynthetic origin that is applied to soils or to plant tissues (usuallyleaves) to supply one or more plant nutrients essential to the growth ofplants in order to increase growth and productivity.

Aqueous Fertilizer, in this invention, is defined as any material ofnatural or synthetic origin that is dissolved in water to form asolution and then applied to soils or to plant tissues (usually leaves)to supply one or more plant nutrients essential to the growth of plantsin order to increase plant growth and productivity. Of particularinterest are aqueous solutions marketed as UAN.

UAN, in this invention, is an aqueous solution comprised of thefertilizer components of urea and ammonium nitrate commonly marketed asUAN followed by a number quantifying the % nitrogen present in theproduct. Example: UAN-30 indicates a composition containing 30% plantavailable nitrogen.

Protic solvent, in this invention, is a solvent containing a hydrogenatom bonded to an electronegative atom such as oxygen and nitrogen orany molecule which contains a dissociable H⁺ (proton).

Polar protic solvent, in this invention, is a subset of polar solventthat have high dielectric constants and high polarity. In this inventionpolar protic solvents are included through the use of the term proticsolvent(s).

Aprotic solvent, in this invention, is a solvent that neither acceptsnor donates H+ (protons) and does not containing dissociable hydrogen.

(aminomethylene)phosphinic acids and bis-(aminomethylene)phosphinicacids, are general names given to a family of compounds containing aphosphinic acid and/or their salts and connected to an amine through amethylene linkage.

Polar aprotic solvent, in this invention, is a subset of aproticsolvents that have high dielectric constants and high polarity. In thisinvention polar aprotic solvents are included through the use of theterm aprotic solvent(s).

AMP acids and their salts are (aminomethylene), di(aminomethylene) andbis-(aminomethylene) phosphinic acids and their salts which are thereaction product of a) hypophosphoric acid, b) one or more aldehydesselected from the group consisting of i) formaldehyde, ii)paraformaldehyde and iii) 1,3-trioxane and c) one or more membersselected from the group consisting of i) ammonia ii) ammonium hydroxideiii) one or more organo amines containing an aldehyde reactive nitrogen.

Nitrogen source is a general term used to identify compounds that areutilized to provide nitrogen for plants including but not limited tourea, manure, compost, urea formaldehyde reaction products,urea/ammonia/formaldehyde reaction products, ammonium sulfate, ammoniumnitrate, diammonium phosphate, anhydrous ammonia, urea/ammonium nitrateaqueous solutions (UAN) and other urea aqueous solutions.

Mobile liquid form of nitrogen sources is a general description of aliquid form of a nitrogen source that is mobile including but notlimited to aqueous dispersions, pressurized ammonia and molten urea andmolten modified urea.

OPCF is an abbreviation for Organo Polycarboxylate functionalities.

Organo Polycarboxylate Functionalities: is a general term used todescribe an organic compound with a minimum of three carboxylate groupswherein the polycarboxylate compounds are comprised of one or moremembers selected from the group consisting of a) organicpolymers/oligomers containing polycarboxylate functionalities and b)amino carboxylate functionalities wherein the carboxylatefunctionalities are comprised of one or more members selected from thegroup consisting of a) carboxylic acids, b) carboxylic anhydrides c)carboxylic imides, d) one or more carboxylic esters and e) carboxylicacid salt wherein said salt is derived from the reaction of aneutralizing agent.

Neutralizing agents are comprised of alkaline compounds that contain oneor more members selected from the group consisting of a) one or moremetal cations selected from the group consisting of Na, K, Mg, Ca, Fe,Zn, Mn, Cu, Co, Mo and Ni and b) one or more of nitrogen containingcompounds selected from the group consisting of ammonia, ammoniumhydroxide and organoamines

NOSDS is an abbreviation for a non-aqueous organo solvent deliverysystem.

NAPAOL (non-aqueous polar, aprotic organo liquid): an aprotic NOSDS(non-aqueous organo solvent delivery system) that is used specificallyas the reaction medium.

Nitrogen source aqueous solution is a generic term to describe anitrogen source that has been dissolved in water including but notlimited to urea, urea and/or ammonium nitrate (UAN) and other mixednitrogen sources.

Modified urea is a generic term used to describe urea that has beenchemically modified with one or more reactive agents selected from thegroup consisting of a) formaldehyde, modified formaldehydes includingbut not limited to paraformaldehyde, trioxane, methoxy cappedformaldehyde reaction products including but not limited to1,3,4,6-Tetrakis(methoxymethyl)glycoluril andN,N,N′,N′,N″,N″-Hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamineand/or may contain one or more bio-active agents.

Bio-active agent is a generic term used to describe compounds manmadeand products of natural processes that imparts one or more properties tosoil selected from the group consisting of urease inhibition,nitrification inhibition, de-nitrification inhibition, pesticides,herbicides, fungicides and insecticides.

Biologics are bio-active agents that are specified as a differentcategory due to their definition as naturally occurring substances,substances produced by natural processes such as fermentation and/orextracts of naturally occurring substances.

AMP: (aminomethyl) phosphinic acids and their salts

NAPAOL: (non-aqueous polar, aprotic organo liquid): an aprotic NOSDS(non-aqueous organo solvent delivery system) that is used specificallyas the reaction medium.

Treated nitrogen source: a composition comprising a nitrogen source andbiologically active agents and/or biologics added either through acoating application or added to the nitrogen source during the nitrogensource's production process either in the melt portion or applied to thenitrogen source during the formation of the nitrogen source's granule.

Stable liquid Solutions: flowable compositions wherein the actives arecompletely dissolved within a NOSDS and do not separate or show morethan 5% sedimentation over a period of 30 days.

Substantially free of Water: a composition comprised of less than 5%water.

Ranges are used to describe a range of values and are defined as when arange is discussed, it is contemplated and therefore within the scope ofthe invention that any number that falls within that range iscontemplated as an end point generating a plurality of sub-ranges withinthat range. For example if a range of 1-10 is given, 2, 3.1, 4.8, 5, 6,7, 8, and 9 are contemplated as end points to generate a sub-range thatfit within the scope of the enumerated range.

Percentage (%) is based on weight in a composition.

Particle(s) is a generic term which describes the physical condition ofany solid nitrogen sources such as granules, prills, and powder.

Phosphinic acid organo amines is a generic terms which describesbis(aminomethyl)phosphinic acids,aminomethyl(alkylaminomethyl)phosphinic acids, anddi(alkylaminomethy)phosphinic acids. The salts of each of the individualphosphinic acids organo amines are optional.

In an embodiment, the present invention relates to an additive thatimparts to liquid or solid manmade fertilizer, manure, waste or compostan increased longevity of plant available nitrogen in the soil whereinthe additive is a dry, flowable composition created by coatingnitrification inhibitors with urease inhibitors dissolved in NOSDS atconcentrations of urease inhibitors of 50-90%. In a variation,nitrification inhibitors can be coated with urease inhibitors dissolvedin a blend of polar aprotic and protic solvents. The resulting coatednitrification inhibitor can then be mixed with granular, natural orsynthetic, fertilizer or added to fertilizer combination of urea andammonium nitrate that has been dissolved in water (commercial name ofUAN).

The combination of nitrification and urease inhibitors will inhibitbiological oxidation of ammonia by soil microbes, such as Nitrosomonasbacteria and inhibit the enzymatic action of urease slowing theconversion urea nitrogen to ammoniacal nitrogen. In one embodiment,improved delivery formulations have been developed that delivereffective levels of urease inhibitors as a coating on nitrificationsinhibitors that increase the plant available nitrogen longevity of UANsolutions and granular fertilizers when applied to soil. It has beenfound that the delivery formulations of the present invention provide aliquid vehicle to deliver an even, non-clumping application of thedesired urease inhibitors to the nitrification inhibitor surfaces. Thesenew delivery formulations for coating nitrification inhibitors are basedon a Non-aqueous Organic Solvent Delivery System (NOSDS), which improvestorage life of urease inhibitors such as alkyl thiophosphoric triamidesover those formulations containing greater than 1% water. In fact,because of the present invention, one can now deliver the inhibition ofthe oxidation of ammonia to nitrates and the conversion of urea toammonia in an additive that easily dissolves into a liquid fertilizersuch as UAN, and as a dry additive for granular fertilize.

In one embodiment, the improved delivery systems of the presentinvention can be utilized as a vehicle to impart a coating of a ureaseinhibitor to the surface of nitrification inhibitors comprised of one ormore selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, ammonium thiosulfate, 1-mercapto-1,2,4-triazole,dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine. The combined impact of using anitrification inhibitor coated with a urease inhibitor that is dissolvedin a Non-aqueous Organic Solvent Delivery System (NOSDS) with enhancedstorage stability lowers the cost of fertilizer by delivering optimizedand homogeneous levels of both inhibitors improving the longevity ofnitrogen in the soil.

In an embodiment, the present invention relates to an additive thatimparts to liquid or solid manmade fertilizer, manure, waste or compostan increased longevity of plant available nitrogen in the soil whereinthe additive is a dry, flowable composition created by coatingdicyandiamide with a N-alkyl thiophosphoric triamide dissolved in anon-aqueous organo liquid system at concentrations of the N-alkylthiophosphoric triamide in the solvent of 50-90%. The resulting coatedDCD can then be mixed with natural or synthetic granular fertilizer oradded to fertilizer combination of urea and ammonium nitrate that hasbeen dissolved in water (commercial name of UAN), which will inhibitbiological oxidation of ammonia by soil microbes, such as Nitrosomonasbacteria and inhibit the enzymatic action of urease slowing theconversion urea nitrogen to ammoniacal nitrogen.

In one embodiment, the present invention relates to liquid formulationscomprised of urease inhibitors and a Non-aqueous Organic SolventDelivery System (NOSDS) and is designed to coat nitrification inhibitorgranules with an effective level of urease inhibitor(s) utilizing simpleapplication equipment such as mixers, blenders and tumblers

In an embodiment, an additive that imparts to liquid or solid manmadefertilizer, manure, waste or compost an increased longevity of plantavailable nitrogen in the soil wherein the additive is a dry, flowablecomposition comprising one or more solid nitrification inhibitor(s)coated with a liquid formulation comprised of one or more ureaseinhibitor(s) that have been solubilized within a non-aqueous organosolvent delivery system (NOSDS) wherein the NOSDS is further comprisedof one or more aprotic and protic solvent(s)

wherein said aprotic solvent(s) is one or more members selected from thegroup consisting of:

-   -   a. dimethyl sulfoxide    -   b. and one or more sulfoxide(s) selected from the group        consisting of dialkyl, diaryl, or alkylaryl sulfoxide(s)        selected from the formula structure:

R⁹S(O)xR¹⁰

-   -    wherein        -   i. R⁹ and R¹⁰ are each independently a C₁-C₆alkylene group,            an aryl group or C₁-C₃ alkylenearyl group        -   ii. or R⁹ and R¹⁰ with the sulfur to which they are attached            form a 4 to 8 membered ring wherein R⁹ and R¹⁰ together are            a C₁-C₆alkylene group which optionally contains one or more            atoms selected from the group consisting of O, S, Se, Te, N,            and P in the ring        -   iii. and x is 1 or 2    -   c. one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate    -   d. one or more polyols capped with acetate or formate wherein        the polyol portion selected from the group consisting of        ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,        butylene glycol, trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol and sorbitan, glucose, fructose,        galactose and glycerin    -   e. one or more alkylene glycol alkyl ethers acetates selected        from the group consisting of dipropylene glycol methyl ether        acetate, tripropylene glycol methyl ether acetate, and        tripropylene glycol butyl ether acetate    -   f. one or more diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate,    -   g. one or more alkyl pryrrolidone selected from the group        consisting of 1-Methyl-2-pyrrolidone and cyclohexylpyrrolidone,    -   h. one or more selected from the group consisting of        dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone, isophorone, hexamethylphosphoramide,        1,2-dimethyloxyethane, 2-methoxyethyl ether and limonene    -   i. One or more trialkyl phosphates selected from the group        consisting of triethyl phosphate and tributyl phosphate    -   and wherein said protic solvent is one or more members selected        from the group consisting of:    -   a. one or more alcohols selected from the group consisting of        the family of C₁-C₁₀alkanols    -   b. one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin    -   c. one or more polyalkylene glycols selected from the group        consisting of poly(C₁-C₁₀ alkylene) glycols,    -   d. isopropylidene glycerol    -   e. one or more alkylene glycol alkyl ethers selected from the        formula structure:

-   -    wherein        -   i. R¹ is one or more members selected from the group            consisting of CH₃, C₂H₅, C₃H₇ and C₄H₉        -   ii. R² is one or more members selected from the group            consisting of H            -   and

-   -   -   -   wherein                -   (1) R⁴ is one or more members selected from the                    group consisting of H and CH₃,                -   (2) and f is an integer between 1 and 15,

        -   iii. wherein R³ is one or more members selected from the            group consisting of H and CH₃

    -   f. one or more alkyl lactates selected from the group consisting        of ethyl, propyl and butyl lactate

    -   g. one or more alkanolamines selected from the group consisting        of alkanolamines selected from the formula structure:

-   -    wherein        -   i. R⁵ is one or more members selected from the group            consisting of C₂H₄OR⁸ and C₃H₆OH        -   ii. R⁶ is: H, C₂H₄OR⁸ and C₃H₆OH        -   iii. R⁷ is one or more members selected from the group            consisting of H, C₂H₄OR⁸ and C₃H₆OH            -   wherein                -   (1) R⁸ is (C₂H₄O)_(g)H                -    wherein                -    (a) g is an integer between 1-10    -   h. and glycerol carbonate    -   such that said dry, flowable additive's composition weight        percent comprises 80-99% nitrification inhibitor, 18-0.5% urease        inhibitor and 10-0.2% NOSDS wherein said NOSDS's composition        consist of a weight percent range for protic to aprotic solvents        of 0%:100% to 100%:0%.

Thus in one embodiment, the present invention relates to improvedcompositions of a solution of urease inhibitor(s) in a non-aqueousorgano solvent delivery system for coating the surface of nitrificationinhibitor(s) that:

-   -   Are environmentally safe;    -   Have flashpoints above 145° F.;    -   Are inherently rated safe for contact with humans and animals;    -   Forms a liquid solution at 20-70° C. of urease inhibitors        comprising a composition consisting of a % weight ratio of NOSDS        at 50-10% to urease inhibitors at 50-90 for coating the surfaces        of nitrification inhibitors with urease inhibitors    -   Provides an even and effective coating of urease inhibitor to        the surfaces of nitrification inhibitors granules and powders        while not causing clumping of the granules or powder.    -   Assisting the coated nitrification inhibitor granules and        powders to easily dissolve in water or aqueous fertilizers        resulting in a clear and stable solution ready for application        to plants and to soil.

In one embodiment, the present invention relates to compositions havingat least 0.5-20% of active urease inhibitor on the surface ofnitrification inhibitors.

In one embodiment, it has also been discovered that while variousorgano-liquids might meet some of the above criteria, the deliverysystem of the present invention can be optimized to provide aformulation with a high concentration of inhibitors while maintaining achill point of 20° C. to 60° C. by combining two or more organo-liquidsin a solvating system.

In an embodiment, a method of preparing the additive comprises: a.Suspending or making a solution of urease inhibitor(s) in a NOSDS attemperatures 20-70° C. wherein the urease inhibitor is in the % weightrange of about 50 to 90%; b. In a separated vessel, placing powder orgranular nitrification inhibitor(s) under agitation at 20-70° C.; c.Slowly adding the slurry or solution of the urease inhibitor(s) from “a”to powder or granules of nitrification inhibitor(s) and mixing until theurease inhibitor(s) in NOSDS has uniformly coated the nitrificationinhibitor(s) wherein the composition's weight percent comprises 80-99%nitrification inhibitor(s), 18-0.5% urease inhibitor(s) and 10-0.2%NOSDS. In a variation the additive's composition comprises adding a flowmodifier to improve handling properties and wherein the additive is adry, flowable solid.

In an embodiment, the improved delivery formulations have been developedthat can impart effective levels of urease inhibitors to the surface ofnitrification inhibitors that increase the nitrogen longevity in thesoil. These formulations not only provide a liquid vehicle to deliver aneven, non-clumping application of the desired inhibitors to thenitrification granules, but it has been discovered that formulationsbased on non-aqueous solvating systems improve the storage life of theimportant urease inhibitors, such as alkyl thiophosphoric triamides.Alkyl thiophosphoric triamides have been shown to be extremely effectiveurease inhibitors but suffer from degradation upon storage if exposed tomoisture. Thus, in one embodiment the present invention relates tocompositions that are substantially free of water.

In an embodiment, the composition of the liquid urease inhibitorconcentrate further comprises of one or more of the group consisting of:

-   -   Nitrification inhibitor(s);    -   NOSDS    -   Additives such as but not limited to surfactants, buffers,        fragrance/odor masking agents, colorants, micro-nutrients,        and/or flow modifiers such as silica.

In one embodiment, during the process of coating of the nitrificationinhibitors with the liquid urease inhibitor concentrate, one mayoptionally include one or more of the group consisting of surfactants,buffers, fragrance/odor masking agents, colorants, micro-nutrients,and/or flow modifiers.

In one embodiment, the solvating system of the present invention is aNOSDS, which comprises one or more of the group consisting of: dimethylsulfoxide, sulfolane, tetramethylene sulfoxide dimethylacetamide,dimethylformamide hexamethylphosphoramide, triethylphosphate, tributylphosphate, propylene carbonate, ethylene carbonate, butylene carbonate,N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether,cyclohexylpyrrolidone, ethyl lactate, and 1,3dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol,butylene glycol, trimethylol propane, pentaerythritol, glycerin,trimethylol ethane, polyethylene glycol, polypropylene glycol,polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methylether, Tripropylene glycol butyl ether, acetate and/or fumarate cappingof glycols which include but are not limited to the following glycols:

-   -   ethylene glycol, propylene glycol, butylene glycol, trimethylol        propane, pentaerythritol, glycerin, trimethylol ethane,        polyethylene glycol, polypropylene glycol,        polyethylene/polypropylene glycol co-polymer, Tripropylene        glycol methyl ether, Tripropylene glycol butyl ether.

Additionally, the NOSDS of the present invention may be comprised of oneor more of the group consisting of:

-   -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the        formulations;    -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        nitrification inhibitor granules; and    -   Buffering agents.

In an embodiment, the liquid urease inhibitor concentrate may beutilized to coat nitrification inhibitors comprised of one or more ofthe group consisting of 2-chloro-6-trichloromethyl)pyridine,4-amino-1,2,4-6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazineCL-1580, dicyandiamide (DCD), thiourea, ammonium thiosulfate,1-mercapto-1,2,4-triazole, dimethylpyrazole organic and inorganic saltsand 2-amino-4-chloro-6-methylpyrimidine.

In one embodiment, the formulations of the present invention may usedicyandiamide as the nitrification inhibitor that is coated with aformulation comprised of dimethyl sulfoxide and n-butyl thiophosphorictriamide (NBPT). Both actives also provide the secondary benefit ofbeing slow release fertilizers. In one embodiment, the fertilizeradditive provides for compositions that are substantially free of water.The present invention is also advantageous relative to other systemsthat have used cost prohibitive coating/adhesion technologies.

In one embodiment of the present invention, the utilization of lowtemperature application allows for non-clumping of the coatednitrification inhibitor granules. Moreover, the use of low temperatureapplication of a coating comprised of NOSDS and a urease inhibitorlimits the thermal degradation of the components. In one embodiment, thepresent invention allows for the additional benefit of coating utilizingsimple equipment such as blenders, tumbler and mixers and does notrequire molten urea, high temperature, addition of adhesives or coatingof a urea formaldehyde polymer with a urease inhibitor. The innovativeadditive results in urease coated nitrification inhibitor granules thatare easily soluble in water and aqueous fertilizers resulting in moreeven distribution of the urease and nitrification inhibitor when appliedto soil or plants.

In an embodiment, the formulation(s) of the present invention maycontain one or more nitrification inhibitors coated with one or moreurease inhibitors dispersed within the NOSDS.

In an embodiment, the innovative additive's composition comprises one ormore urease inhibitors selected from the group consisting of

-   -   a. One or more alkyl phosphoric amide selected from the formula        structure:

-   -    wherein:        -   i. R₁₈ is one or more members selected from the group            consisting of CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₆H₅,            C₇H₇, OX₄, OCH3, OC₂H₅, OC₃H₇, OC₄H₉, OC5H11, OC₆H₁₃, and            HNR₂₁            -   wherein                -   (1) R₂₁ is one or more members selected from the                    group consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁                    and C₆H₁₃                -   (2) X₄ is one or more members selected from the                    group consisting of                -    (a) H, Na, Li and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.        -   ii. R₁₉ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,        -   iii. R₂₀ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃        -   iv. Z₃ is one or more members selected from the group            consisting of Oxygen and Sulfur.    -   b. One or more (aminomethylene)phosphinic acids and their salts        selected by the formula structure:

-   -    wherein:        -   i. R₁₁ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₁            and C₈H₁₇,        -   ii. R₁₂ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,        -   iii. R₁₃ is one or more members selected from the group            consisting of H, O—X₃, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,            C₇H₁₅, C₈H₁₇, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁, OC₆H₁₃,            OC₇H₁₅ and OC₈H₁₇            -   wherein                -   (1) X₃ is one or more members selected from the                    group consisting of selected from the group                    consisting of:                -    (a) H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni                    and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.        -   iv. X₁ is one or more members selected from the group            consisting of            -   -    (a) H, Na, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni, Li                    and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.                -    v. Z₁ is one or more members selected from the                    group consisting of Oxygen and Sulfur.    -   c. and one or more bis-(aminomethylene)phosphinic acids and        their salts selected from the formula structure:

-   -    wherein:        -   i. R₁₄ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅            and C₈H₁₇        -   ii. R₁₅ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃        -   iii. R₁₆ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅            and C₈H₁₇        -   iv. R₁₇ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃        -   v. X₂ is one or more members selected from the group            consisting of            -   -    (a) H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni                    and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.        -   vi. Z₂ is one or more members selected from the group            consisting of Oxygen and Sulfur.

In a variation, the additive's composition comprises the ureaseinhibitor N-(n-butyl) thiophosphoric triamide.

In one embodiment, the present invention relates to using a lowtemperature dispersion procedure (20° C.-70° C.) with one or morephosphoric triamides in a formulation. In one variation, this lowtemperature procedure and the application of the formulation to thesurface of pre-formed nitrification inhibitor granules prevents thermaldegradation of these phosphoric triamides.

In an embodiment, nitrification inhibitor granules can be charge to aribbon blender and warmed to 30-70° C. A solution comprised of a ureaseinhibitor, a colorant and a NOSDS can be sprayed on the surface of thenitrification inhibitor while under agitation and mixed until ahomogeneous coating can be observed. A flow aid comprised of one or morefrom the group consisting of silicas, nonionic surfactants, soaps,inorganic powders, or nonionic surfactants may be added to improve theflow and/or the dispersability of the powder. In a variation, thetemperature of the NOSDS and urease inhibitor based product can beheated to 70° C. max

In an embodiment, the innovative additive can be applied to soil ineither a liquid or granular form to provide improved nitrogen retentionin the soil for uptake for plant life.

In an embodiment, the innovative additive's composition furthercomprises an aqueous solution of the 0.1-10 weight % of said additiveadded to manure, waste or compost. In a variation, the addition of theaqueous solution of the additive can be applied to manure, waste orcompost by automated spray or metering system or by manual sprayer toimprove the longevity of the nitrogen content of these organicfertilizers.

In an embodiment, the present invention is based on urease inhibitorcoating on the surface of nitrification inhibitors comprising of one ormore of the group consisting of 2-chloro-6-trichloromethyl)pyridine,4-amino-1,2,4-6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazineCL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole,ammonium thiosulfate, dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine. In an embodiment, the ureaseinhibitor coating on nitrification inhibitors is achieved through theliquid urease inhibitor concentrate composition comprised of ureaseinhibitors from the group consisting of one or more of a) phosphorictriamides, thiophosphoric triamides and alkylated thiophosphorictriamides, wherein the alkylated thiophosphoric triamides has one ormore alkyl groups that independently contain between 1 and 6 carbonatoms, b) (aminomethylene)phosphinic acids and their salts and c)bis-(aminomethylene)phosphinic acids and their salts.

In an embodiment, the composition may comprise one or more ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, and/or flow modifiers.

In an embodiment, the composition is substantially free of water.

In one embodiment, the additive relates to liquid formulations comprisedof NBPT and a Non-aqueous Organic Solvent Delivery System (NOSDS) and isdesigned to coat nitrification inhibitor granules with an effectivelevel of NBPT utilizing simple application equipment such as mixers,blenders and tumblers.

In an embodiment the NOSDS is comprised of aprotic and protic solventswherein

-   -   said protic solvent(s) is selected from of one or more of the        group consisting of: 1) an alcohol from the family of C1-10        alkanols, 2) one or more polyols from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin, 3) poly(C1-10 alkylene) glycols, 4) one or more        alkylene glycols from the group consisting of ethylene glycol,        1,3 propylene glycol, 1,2 propylene glycol, and butylene        glycol, 5) isopropylidene glycerol 6) one or more alkylene        glycol alkyl ethers represented by the structure:

-   -   Wherein        -   R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉

-   -   -   R² is: H or        -   R³ is: H or CH₃        -   R⁴ is H and/or CH₃

    -   And f is an integer between 1 and 15,

    -   7) one or more alkyl lactates from the group consisting of        ethyl, propyl and butyl lactate, 8) one or more alkanolamines        represented by the structure:

-   -   Wherein    -   R⁵ is: C₂H₄OR⁸ or C₃H₆OH    -   R⁶ is: H, C₂H₄OR⁸ or C₃H₆OH    -   R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH    -   R⁸ is: (C₂H₄O)_(g)H    -   And g is an integer between 1 and 10    -   and 9) glycerol carbonate.        b) and/said aprotic solvent(s) is selected from the group        consisting of 1) dimethyl sulfoxide and/or 2) dialkyl, diaryl,        or alkylaryl sulfoxide(s) having the formula:    -   R⁹S(O)xR¹⁰    -   wherein R⁹ and R¹⁰ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R⁹ and R¹⁰ with the        sulfur to which they are attached form a 4 to 8 membered ring        wherein R⁹ and R¹⁰ together are a C₁₋₆ alkylene group which        optionally contains one or more atoms selected from the group        consisting of O, S, Se, Te, N, and P in the ring and x is 1 or        2,    -   3) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and/or tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters consisting of dimethylsuccinate, dimethyl adipate,        diethyl glutarate, and dimethyl glutarate, 8)        dimethylacetamide, 9) dimethylformamide, 10)        dimethyl-2-imidazolidinone, 11) 1-methyl-2-pyrrolidone, 12)        hexamethylphosphoramide, 13) 1,2-dimethyloxyethane, 14)        2-methoxyethyl ether, 15)cyclohexylpyrrolidone and 16) limonene.

In a variation, the additive that imparts to liquid or solid manmadefertilizer, manure, waste or compost an increased longevity of plantavailable nitrogen wherein the additive is a dry, flowable compositioncomprising one or more solid nitrification inhibitor(s) coated with aliquid formulation comprised of one or more urease inhibitor(s) thathave been solubilized within a non-aqueous organo solvent deliverysystem (NOSDS) wherein the NOSDS is comprised of one or more aproticsolvents selected from the group consisting of 1) dimethyl sulfoxideand/or 2) dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:

-   -   R⁹S(O)xR¹⁰    -   wherein R⁹ and R¹⁰ are each independently a C₁₋₆ alkylene group,        an aryl group, or C¹⁻³ alkylenearyl group or R⁹ and R¹⁰ with the        sulfur to which they are attached form a 4 to 8 membered ring        wherein R⁹ and R¹⁰ together are a C alkylene group which        optionally contains one or more atoms selected from the group        consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2        wherein the composition's weight percent is 80-99% nitrification        inhibitor, 18-0.5% urease inhibitor and 10-0.2% polar aprotic        solvent(s).

In one embodiment, the liquid urease inhibitor concentrate of thepresent invention relates to liquid formulations comprised of NBPT and aNon-aqueous Organic Solvent Delivery System (NOSDS) and is designed tocoat nitrification inhibitor granules with an effective level of NBPTutilizing simple application equipment such as mixers, blenders andtumblers. In an embodiment the NOSDS is comprised of one or moreselected from the group consisting of:

-   -   dimethyl sulfoxide, sulfolane, tetramethylene sulfoxide        dimethylacetamide, dimethylformamide hexamethylphosphoramide,        triethylphosphate, tributylphophate, propylene carbonate,        ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone,        1,2-dimethyloxyethane, 2-methoxyethyl ether,        cyclohexylpyrrolidone, ethyl lactate, and 1,3        dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene        glycol, butylene glycol, trimethylol propane, pentaerythritol,        glycerin, trimethylol ethane, polyethylene glycol, polypropylene        glycol, polyethylene/polypropylene glycol co-polymer,        tripropylene glycol methyl ether, tripropylene glycol butyl        ether, acetate and/or fumarate capping of glycols which include        but are not limited to the following glycols:        -   ethylene glycol, propylene glycol, butylene glycol,            trimethylol propane, pentaerythritol, glycerin, trimethylol            ethane, polyethylene glycol, polypropylene glycol,            polyethylene/polypropylene glycol co-polymer, tripropylene            glycol methyl ether, and tripropylene glycol butyl ether.

In an embodiment, the present invention relates to nitrificationinhibitor additives. In one embodiment, the nitrification inhibitoradditive comprises one or more one or more urease inhibitors dispersedin a NOSDS.

In an embodiment, the additive comprises one or more urease inhibitorsthat are selected from the group consisting of a) phosphoric triamides,b) thiophosphoric triamides, c) alkylated thiophosphoric triamides,wherein the alkylated thiophosphoric triamides has one or more alkylgroups that independently contain between 1 and 6 carbon atoms, d)(aminomethylene)phosphinic acids and their salts and e)bis-(aminomethylene)phosphinic acids and their salts.

In an embodiment, the present invention relates to making compositionsand coating nitrification inhibitors. In one embodiment, the presentinvention relates to a method of making a composition to be coated on anitrification inhibitor, wherein the method comprises:

-   -   1) heating a mixture comprising of a NOSDS and one or more        urease inhibitors that are selected from the group consisting        of a) phosphoric triamides, b) thiophosphoric triamides, c)        alkylated thiophosphoric triamides, wherein the alkylated        thiophosphoric triamides has one or more alkyl groups that        independently contain between 1 and 6 carbon atoms, d)        (aminomethylene)phosphinic acids and their salts and e)        bis-(aminomethylene)phosphinic acids and their salts.    -   2) to effectuate mixing of the mixture;    -   3) holding the mixture to a temperature that is fluid and that        optionally allows addition of one or more of surfactants,        buffers, fragrance/odor masking agents, colorants,        micro-nutrients, and/or flow modifiers.

In an embodiment, the method comprises further adding the composition tocoat a nitrification inhibitor utilizing simple blending equipment. Thecoated nitrification inhibitor can then be added to a UAN aqueoussolution at levels of 0.5-5% resulting in a clear, stable solution thatcan then be applied to the soil and as a foliar application.

In one variation, the additive's composition comprises one or morecoated nitrification inhibitors selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine. In one embodiment, the additive hasa composition that is substantially free of water.

In another embodiment, the nitrification inhibitor coated with a ureaseinhibitor that has been dissolved in a NOSDS is added to an aqueousfertilizer such as a UAN at levels of 0.025-5%.

In an embodiment, a composition consisting of nitrification inhibitor(s)coated with an urease inhibitor that has been solubilized with a NOSDSsuch that the composition's weight percent is 80-99% nitrificationinhibitor, 18-0.5% urease inhibitor and 10-0.1% NOSDS. In one variationthe NOSDS is dimethyl sulfoxide. In another variation the nitrificationinhibitors comprise one or more from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine. In another variation, the ureaseinhibitor comprises an alkylthiophosphoric triamide.

In an embodiment, the dry, flowable additive can be added to molten ureaat a rate of additive to urea 4 to 20 lbs additive/ton of urea. In avariation, the additive/urea combination can be further processed intogranules or prills containing urea with the required amount ofnitrification and urease inhibitors to effective extend the longevity ofplant available nitrogen in the soil.

Fertilizer coating technology utilizes liquid solutions of inhibitors toimpart to the coated urea longevity of plant available nitrogen in thesoil. However, this technology has limitations as the application levelapproaches 0.75% of the liquid coating on urea. Higher % coating levelscauses the urea to become wet negatively impacting the coated ureaprocessability in mixing and application equipment with the formation ofclogs and high level of deposition of the fertilizer requiring morefrequent cleaning and the formation of clumps of fertilizer impactingevenness of fertilizer application to the soil. In an embodiment, % NBPTcan be dissolved in % DMSO and then coated on % DCD particle size0.05-100 microns. In a variation, this innovative additive can be mixedwith urea at levels of 5-20 lbs of additive/ton of urea to meet theminimum effective levels of DCD and NBPT required to extend thelongevity of plant available nitrogen in the soil. In another variation,the small particle size of the additive allows better adhesion to theurea granule or prill. In another variation, the additive is a dry,flowable powder and will not negatively impact the processibility ofurea during the addition process or the application of the urea to thesoil.

In an embodiment, the innovative additive can be dissolved in water atweight % of 0.1-5% of the mixture and then easily sprayed onto naturalfertilizers such as manure to reduce loss of “N” due to microbialactivity. Using a aqueous delivery system for natural fertilizersresults in lower cost versus solvent based liquid inhibitors and can besafely applied by automated spraying systems.

In an embodiment, the innovative additive can be easily dissolved intoliquid fertilizer systems such as UAN utilizing simple mixing equipment.at application levels of 0.05-5.0%. In a variation, the innovativeadditive level in a liquid fertilizer can be 0.5-3%. In an embodiment,the present invention provides for a composition that is easy todissolve resulting in a clear, stable solution in order to insurehomogeneity of the inhibitors throughout the aqueous fertilizer andwhich can deliver the required levels of urease and nitrificationinhibitors in an economically and homogeneous manner to plants and tothe soil while technologies utilizing a urea formaldehyde polymer thatis coated with NBPT and then mix with DCD powder will have poorsolubility in a UAN solution and results in an uneven application levelof inhibitors.

In an embodiment, an additive that imparts to liquid or solid manmadefertilizer, manure, waste or compost an increased longevity of plantavailable nitrogen in the soil wherein the additive is a dry, flowablecomposition comprising one or more solid nitrification inhibitor(s)coated with a liquid formulation comprised of one or more ureaseinhibitor(s) that have been solubilized within a non-aqueous organosolvent delivery system (NOSDS) wherein the NOSDS is comprised of one ormore aprotic organo solvents selected from the group consisting of:

-   -   a. dimethyl sulfoxide    -   b. and one or more sulfoxide(s) selected from the group        consisting of dialkyl, diaryl, or alkylaryl sulfoxide(s)        selected from the formula structure:

R⁹S(O)xR¹⁰

-   -    wherein        -   i. R⁹ and R¹⁰ are each independently a C₁-C₆ alkylene group,            an aryl group or C₁-C₃ alkylenearyl group        -   ii. or R⁹ and R¹⁰ with the sulfur to which they are attached            form a 4 to 8 membered ring wherein R⁹ and R¹⁰ together are            a C₁-C₆ alkylene group which optionally contains one or more            atoms selected from the group consisting of O, S, Se, Te, N,            and P in the ring        -   iii. and x is 1 or 2    -   and wherein the NOSDS optional further comprised of one or more        aprotic and protic solvents wherein the aprotic solvent(s) is        one or more members selected from the group consisting of:    -   a. one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate    -   b. one or more polyols capped with acetate or formate wherein        the polyol portion selected from the group consisting of        ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,        butylene glycol, trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol and sorbitan, glucose, fructose,        galactose and glycerin    -   c. one or more alkylene glycol alkyl ethers acetates selected        from the group consisting of dipropylene glycol methyl ether        acetate, tripropylene glycol methyl ether acetate, and        tripropylene glycol butyl ether acetate    -   d. one or more diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate,    -   e. one or more alkyl pryrrolidone selected from the group        consisting of 1-Methyl-2-pyrrolidone and cyclohexylpyrrolidone,    -   f. one or more selected from the group consisting of        dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone, isophorone, hexamethylphosphoramide,        1,2-dimethyloxyethane, 2-methoxyethyl ether and limonene    -   g. One or more trialkyl phosphates selected from the group        consisting of triethyl phosphate and tributyl phosphate    -   and wherein said protic solvent is one or more members selected        from the group consisting of:

a. one or more alcohols selected from the group consisting of the familyof C₁-C10 alkanols

-   -   b. one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin    -   c. one or more polyalkylene glycols one or more members selected        from the group consisting of poly(C₁-C₁₀ alkylene) glycols,    -   d. isopropylidene glycerol    -   e. one or more alkylene glycol alkyl ethers selected from the        formula structure:

-   -    wherein        -   i. R¹ is one or more members selected from the group            consisting of CH₃, C₂H₅, C₃H₇ and C₄H₉        -   ii. R² is one or more members selected from the group            consisting of H            -   and

-   -   -   -   wherein                -   (1) Where R⁴ is one or more members selected from                    the group consisting of H and CH₃                -   (2) and f is an integer between 1 and 15,

        -   iii. wherein R³ is one or more members selected from the            group consisting of H and CH₃

    -   f. one or more alkyl lactates selected from the group consisting        of ethyl, propyl and butyl lactate

    -   g. one or more alkanolamines selected from the group consisting        of alkanolamines selected from the formula structure:

-   -    wherein        -   i. R⁵ is one or more members selected from the group            consisting of C₂H₄OR⁸ and C₃H₆OH        -   ii. R⁶ is: H, C₂H₄OR⁸ and C₃H₆OH        -   iii. le is one or more members selected from the group            consisting of H, C₂H₄OR⁸ and C₃H₆OH            -   wherein                -   (1) R⁸ is (C₂H₄O)_(g)H                -    wherein                -    (a) g is an integer between 1-10    -   h. and glycerol carbonate    -   such that said dry, flowable additive's composition weight        percent comprises 80-99% nitrification inhibitor, 18-0.5% urease        inhibitor and 10-0.2% NOSDS wherein said NOSDS's composition        consist of a weight percent range for protic to aprotic solvents        of 0%:100% to 100%:0%.

In a variation, an additive that imparts to liquid or solid manmadefertilizer, manure, waste or compost an increased longevity of plantavailable nitrogen in the soil wherein the additive is a dry, flowablecomposition comprising one or more solid nitrification inhibitor(s)coated with a liquid formulation comprised of one or more ureaseinhibitor(s) that have been solubilized within a non-aqueous organosolvent delivery system (NOSDS) wherein the NOSDS is comprised of one ormore aprotic solvent(s) wherein said aprotic solvent(s) comprise one ormore selected from of the group consisting of:

-   -   a. dimethyl sulfoxide    -   b. one or more sulfoxide(s) selected from of the groups        consisting of dialkyl, diaryl, and alkylaryl sulfoxide(s)        selected from the formula structure:

R⁹S(O)xR¹⁰

-   -    wherein        -   i. R⁹ and R¹⁰ are each independently a C₁-C₆alkylene group,            an aryl group, and C₁-C₃ alkylenearyl group        -   ii. or R⁹ and R¹⁰ with the sulfur to which they are attached            form a 4 to 8 membered ring wherein R⁹ and R¹⁰ together are            a C₁-C₆alkylene group which optionally contains one or more            atoms selected from the group consisting of O, S, Se, Te, N,            and P in the ring        -   iii. and x is 1 or 2    -   such that said dry, flowable additive's composition weight        percent comprises 80-99% nitrification inhibitor, 18-0.5% urease        inhibitor and 10-0.2% aprotic solvent(s). In an embodiment, the        innovative additive's composition comprises one or more        nitrification inhibitor(s) selected from the group consisting of        2-chloro-6-trichloromethyl)pyridine,        4-amino-1,2,4-6-triazole-HCl,        2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide        (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium        thiosulfate, dimethylpyrazole organic and inorganic salts and        2-amino-4-chloro-6-methylpyrimidine.

In a variation, the additive's composition comprises one or morenitrification inhibitor(s) selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, dicyandiamide (DCD), thiourea,ammonium thiosulfate and dimethylpyrazole organic and inorganic salts.

In another variation, the additive's composition comprises thenitrification inhibitor dicyandiamide.

In an embodiment, the innovative additive's composition comprises one ormore urease inhibitors selected from the group consisting of

-   -   a. One or more alkyl phosphoric amide selected from the formula        structure:

-   -    wherein:        -   i. R₁₈ is one or more members selected from the group            consisting of CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₆H₅,            C₇H₇, OX₄, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁, OC₆H₁₃, and            HNR₂₁            -   wherein                -   (1) R₂₁ is one or more members selected from the                    group consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁                    and C₆H₁₃                -   (2) X₄ is one or more members selected from the                    group consisting of                -    (a) H, Na, Li and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.        -   ii. R₁₉ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,        -   iii. R₂₀ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃        -   iv. Z₃ is one or more members selected from the group            consisting of Oxygen and Sulfur.    -   b. One or more (aminomethylene)phosphinic acids and their salts        selected by the formula structure:

-   -    wherein:        -   i. R₁₁ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅            and C₈H₁₇,        -   ii. R₁₂ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,        -   iii. R₁₃ is one or more members selected from the group            consisting of H, O—X₃, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,            C₇H₁₅, C₈H₁₇, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁, OC₆H₁₃,            OC₇H₁₅ and OC₈H₁₇            -   wherein                -   (1) X₃ is one or more members selected from the                    group consisting of selected from the group                    consisting of:                -    (a) H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni                    and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.                -   (2) X₁ is one or more members selected from the                    group consisting of                -    (a) H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni                    and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.        -   iv. Z₁ is one or more members selected from the group            consisting of Oxygen and Sulfur.    -   c. and one or more bis-(aminomethylene)phosphinic acids and        their salts selected from the formula structure:

-   -    wherein:        -   i. R₁₄ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅            and C₈H₁₇        -   ii. R₁₅ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃        -   iii. R₁₆ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅            and C₈H₁₇        -   iv. R₁₇ is one or more members selected from the group            consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃            -   -   (1) X₂ is one or more members selected from the                    group consisting of                -    (a) H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni                    and K,                -    (b) NH₄                -    (c) one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine.        -   v. Z₂ is one or more members selected from the group            consisting of Oxygen and Sulfur.

In a variation, the additive's composition comprises one or more ureaseinhibitors selected from the group consisting of N-(n-butyl)thiophosphoric triamide and (hexylaminomethylene, aminomethylene)phosphinic acid (C₈H₂₀N₂O₂P) and/or its salts wherein said salt isderived from the reaction of a neutralizing agents with the phosphinicacid and wherein said neutralizing agents are comprised of a) one ormore metal cations wherein metal cations are derived from one or moremembers selected from the group consisting of i) elemental metals ii)metal oxides iii) metal hydroxides, iv) metal alkylates and v) metalcarbonates wherein the one or more metal cations' portion of theneutralizing agent is selected from the group consisting of Na, K, Mg,Ca, Fe, Zn, Mn, Cu, Co, Mo and Ni.

In a variation, the additive's composition comprises the ureaseinhibitor N-(n-butyl) thiophosphoric triamide.

In an embodiment, the additive's composition is comprised of ureaseinhibitors that are in a solution within the NOSDS at a weight ratio of50-90% urease inhibitors to 50-10% NOSDS.

In an embodiment, the additive's composition further comprises one ormore biologics selected from the group consisting of:

-   -   i. Bacillus biologics, ii) Azospirillum biologics, iii)        Azobacter biologics iv) Gluconacetobacter biologics, v)        Phosphobacteria, vi) Cyanobacteria, vii) Herbaspirillum, viii)        Burkholderia, ix) Pseudomonas, x) Gluconacetobacter, xi)        Enterobacter, xii) Klebsiella, xiii) Burkholderia, xiv)        Bradyrhiwbium species, xv) Bradyrhiwbium japonicum, xvi)        Rhizobium meliloti, xvii) Laccaria bicolor, xviii) Glomus        imraradices timanita, xix) Actinomyces, xx) Penicillium, xxi)        Mesorhizobiwn cicero, xxii) one or more insecticidal or insect        repellent microbial species and strains selected from the group        consisting of:        -   Telenomus podisi, Baculovirus anticarsia; Trichogramma            pretiosum, Trichogramma gallai, Chromobacterium subtsugae,            Trichoderma fertile, Beauveria bassiana, Beauveria bassiana,            Beauveria bassiana, Paecilomyces ficnwsoroseu!, Trichoderma            harzianum, Verticillium lecanii, lsarfofumosarosea            Lecanicillium muscarium, Streptomyces microflavus, Muscodor            albus,    -   xxiii) one or more nematodal microbial species and strains        selected from the group consisting of:        -   Myrothecium verrucaria, Pasteuria species, Pasteuria            Metarhizium species, Flavobacteriwn species    -   xxiv) Reynoutria sachalinensis    -   xxv) one or more antifungal, antimicrobial and/or plant growth        promoting microbial species and strains selected from a group        consisting of:        -   Gliocladium species, Pseudomonas species (e.g. Pseudomonas            fluorescens, Pseudomonas fluorescens. putida and P.            chlororaphis), Pseudomonas fluorescens VP5, Pseudomonas            diazotrophicus, Enterobacter cloacae, Trichodema species,            Trichoderma virens, Trichoderma atroviride strains,            Coniothyrium minitans, Gliocladium species, Gliocladium            virens, Gliocladium roseum, Trichodemw harzianum species,    -   xxvi) Spore forming species of bacteria;    -   xxvii) Spore forming species of fungi;    -   xxviii) Mycorrhizal organisms including: Laccaria bicolor,        Glomus intraradices, and Amanita species;    -   xxix) Actinomyces species and strains thereof, including:        Streptomyces lydicus, Streptomyces griseoviridis, Streptomyces        griseoviridis, Streptomyces microflavus    -   xxx) Bacillus species and strains thereof, including: Bacillus        itchenifomis, Bacillus megaterium, Bacillus pumilus, Bacillus        amyloliquefaciens, Bacillus licheniformis, Bacillus oleronius,        Bacillus megaterium, Bacillus mojavensis, Bacillus pumilus,        Bacillus subtilis, Bacillus circulans, Bacillus globisporus,        Bacillus firmus, Bacillus thuringiensis,        -   Bacillus cereus, Bacillus amyloliquefaciens, Bacillus fimms            strain I-1582 (Votivo and Nortica; Bayer), Bacillus            licheniformis. Bacillus lichenformis, Bacillus pumilus,            Bacillus subtilis strains, Bacillus subtilis,        -   Bacillus amyloliquefaciens Bacillus pumilus, Bacillus            thuringiensis galleriae, Bacillus thuringiensis susp            kurstaki, Bacillus cereus, Bacillus        -   subtilis, Bacillus thuringiensis, Bacillus sphaericus,            Bacillus megaterium, B. vallismortis,    -   xxxi) Species of Plant Growth Promoting Rhizobacteda (PGPRs} and        strains thereof, including:        -   (1) one or more Gluconacetabacter species selected from the            group consisting of: Gluconacetobacter diazotrophicus a,k.a,            Acetobacter diazatrophicus,        -   (2) one or more Spirillum species selected from the group            consisting of:        -   Spirillmn lipoferum,        -   (3) one or more Azospirillum species selected from the group            consisting        -   of: Herbaspirillwn seropedicae,        -   (4) one or more Azoarcus species        -   (5) one or more Azotobacter species selected from the group            consisting of:        -   Burkholderia, Burkhalderia sp., Paenibacillusp olymyxa,    -   xxxii) N-fixing bacterial species and strains thereof, including        -   (1) one or more Rhizobium species        -   (2) one or more Bradyrhizobium species selected from the            group consisting of: Bradyrhizobium japonicum, Rhizobium            meliloti    -   xxxiii) Microbial species and strains thereof that are known to        improve nutrient        -   use efficiency, including        -   (1) one or more Penicillium species selected from the group            consisting of:        -   Penicillium bilaii, Penicillium bilaji, Mesorhizobium            cicero,    -   xxxiv) Bacterial species and strains thereof from the group        termed Pink-Pigmented Facultative Methylotrophs including        Methylobacterium species.

In an embodiment, the additive's composition further comprisessurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, dispersed nitrification inhibitors and/or flowmodifiers.

In an embodiment, the NOSDS further comprises the following criteria

-   -   a. Is environmentally safe;    -   b. Have flashpoints above 145° F.;    -   c. Is inherently rated safe for contact with humans and animals;    -   d. Forms a liquid solution at 20-70° C. of urease inhibitors        comprising a composition consisting of a % weight ratio of NOSDS        at 50-10% to urease inhibitors at 50-90 for coating the surfaces        of nitrification inhibitors with urease inhibitors    -   e. Provides an even and effective coating of urease inhibitor to        the surfaces of nitrification inhibitors granules and powders        while not causing clumping of the granules or powder.    -   f. Assisting the coated nitrification inhibitor granules and        powders to easily dissolve in water or aqueous fertilizers        resulting in a clear and stable solution ready for application        to plants and to soil.

In an embodiment, the additive's composition further comprises 0.1-10weight % of said dry, flowable additive added to an aqueous fertilizersolution to form a homogeneous and stable composition of ureaseinhibitors, nitrification inhibitors, fertilizer components and water

In an embodiment, the additive's composition further comprises blendswith liquid or solid manmade fertilizer, manure, waste or compost.

In an embodiment, the additive's composition further comprises anaqueous solution of the 0.1-10 weight % of said additive added tomanure, waste or compost.

In an embodiment, the additive's composition consists of <5.0% water.

In an embodiment, a method of preparing the additive comprises: a.Suspending or making a solution of urease inhibitor(s) in a NOSDS attemperatures 20-70° C. wherein the urease inhibitor is in the % weightrange of about 50 to 90%; b. In a separated vessel, placing powder orgranular nitrification inhibitor(s) under agitation at 20-70° C.; c.Slowly adding the slurry or solution of the urease inhibitor(s) from “a”to powder or granules of nitrification inhibitor(s) and mixing until theurease inhibitor(s) in NOSDS has uniformly coated the nitrificationinhibitor(s) wherein the composition's weight percent comprises 80-99%nitrification inhibitor(s), 18-0.5% urease inhibitor(s) and 10-0.2%NOSDS. In a variation the additive's composition comprises adding a flowmodifier to improve handling properties and wherein the additive is adry, flowable solid.

In an embodiment, the stable liquid solutions are designed to be used inconjunction with a nitrogen source or for direct application to the soilto slow or retard the loss of nitrogen in the soil. In an embodiment,these delivery formulations not only provide a liquid vehicle to deliveran even, non-clumping application of [aminomethylene] phosphinic (AMP)acids and their salts along with other desired bio-actives to nitrogensources, but formulations based on NOSDS improve the storage life of theimportant bio-actives, such as alkyl thiophosphoric triamides. Thus, inone embodiment the present invention relates to compositions that aresubstantially free of water.

In an embodiment, the stable liquid solutions comprise a) NOSDS and b)one or more AMP acids and their salts wherein NOSDS is comprised one ormore polar, aprotic solvents selected from the group consisting of:

-   -   a) dimethyl sulfoxide,    -   b) an dialkyl, diaryl, or alkylaryl sulfoxide(s) having the        formula:

R₉S(O)_(x)R₁₀,

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2,    -   c) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate d) 1-Methyl-2-pyrrolidone, e) one or more        organo phosphorous liquids selected from the group consisting of        hexamethylphosphoramide and one or more trialkylphosphates        selected from the group represented by the formula:

-   -   -   wherein:        -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃,        -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃,        -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃,

    -   f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h)        cyclohexylpyrrolidone, and wherein AMP acids and their salts        comprise one or more reaction products of:

    -   a) one or more phosphorous acids and/or their salts represented        by the following structure:

-   -   -   wherein            -   Z₃ is one or more members selected from the group                consisting of oxygen and sulfur and            -   Z₄ is one or more members selected from the group                consisting of oxygen and sulfur,            -   X₁ is selected from one or more of the group consisting                of selected from the group consisting of:                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,

    -   b) one or more aldehydes selected from the group consisting        of i) formaldehyde, ii) paraformaldehyde and iii) 1,3,5-trioxane        and

    -   c) one or more members selected from the group consisting of i)        ammonia ii) ammonium hydroxide iii) one or more organo amines        containing an aldehyde reactive nitrogen selected from the        structure:

-   -   -   wherein R₁₈ is one or more members selected from the group            consisting of: H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,            C₇H₁₅, C₅H₁₂N, C₆H₁₃N₂, C₆H₉N₃, C₆H₇N, C₅H₁₄N₂ and C₈H₁₇,

    -   wherein the resulting composition of the reaction product        contains the following AMPs acid and their salts structures:

    -   a.

-   -   -   wherein:            -   i. R₁₁ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅, C₅H₁₂N, C₆H₁₃N₂, C₅H₁₄N₂, C₆H₉N₃, C₆H₇N and                C₈H₁₇,            -   ii. R₁₂ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   iii. R₁₃ is selected from one or more of the group                consisting of H, O—X₃, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                C₆H₁₃, C₇H₁₅, C₈H₁₇, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC5H11,                OC₆H₁₃, OC₇H₁₅ and OC₈H₁₇,            -   iv. X₃ is selected from one or more of the group                consisting of selected from the group consisting of:                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,            -   v. X₁ is selected from one or more of the group                consisting of                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,            -   vi. Z₁ is selected from one or more of the group                consisting of Oxygen and Sulfur,

    -   b. and one or more di(aminomethylene)phosphinic acids and their        salts selected from the formula structure:

-   -   -   wherein:            -   i. R₁₄ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅, C₆H₁₃N₂, C₅H₁₄N₂, C₆H₉N₃, C₆H₇N and C₈H₁₇,            -   ii. R₁₅ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   iii. R₁₆ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅ and C₈H₁₇,            -   iv. R₁₇ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   v. X₂ is selected from one or more of the group                consisting of                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,            -   vi. Z₂ is selected from one or more of the group                consisting of Oxygen and Sulfur,            -   vii. Z₆ is selected from one or more of the group                consisting of Oxygen and Sulfur,

    -   wherein the weight composition of the stable liquid solution        comprises 20-99% NOSDS and 1-80% AMPs acids and their salts.

In an embodiment, the stable liquid solutions comprise a) NOSDS and b)one or more AMP acids and their salts. In a variation, the stable liquidsolutions can further comprise:

-   -   a) one or more bio-actives selected from the group consisting        of:        -   (1) One or more biologics selected from the group consisting            of:            -   (a) one or more biologics selected from the group                consisting of:                -   i) Bacillus biologics, ii) Azospirillum                    biologics, iii) Azobacter biologics iv)                    Gluconacetobacter biologics, v) Phosphobacteria, vi)                    Cyanobacteria, vii) Herbaspirillum, viii)                    Burkholderia, ix) Pseudomonas, x)                    Gluconacetobacter, xi) Enterobacter, xii)                    Klebsiella, xiii) Burkholderia, xiv) Bradyrhiwbium                    species, xv) Bradyrhiwbium japonicum, xvi) Rhizobium                    meliloti, xvii) Laccaria bicolor, xviii) Glomus                    imraradices timanita, xix) Actinomyces, xx)                    Penicillium, xxi) Mesorhizobiwn cicero, xxii) one or                    more insecticidal or insect repellent microbial                    species and strains are selected from the group                    consisting of:                -    Telenomus podisi, Baculovirus anticarsia;                    Trichogramma pretiosum, Trichogramma gallai,                    Chromobacterium subtsugae, Trichoderma fertile,                    Beauveria bassiana, Beauveria bassiana, Beauveria                    bassiana, Paecilomyces jknwsoroseu, Trichoderma                    harzianum, Verticillium lecanii, lsarfofumosarosea                    Lecanicillium muscarium, Streptomyces microflavus,                    and Muscodor albus,                -   xxiii) one or more nematodal microbial species and                    strains are selected from the group consisting of:                -    Myrothecium verrucaria, Pasteuria species,                    Pasteuria                -    Metarhizium species, and Flavobacteriwn species                -   xxiv) Reynoutria sachalinensis and                -   xxv) one or more antifungal, antimicrobial and/or                    plant growth promoting microbial species and strains                    are selected from the group consisting of                    Gliocladium species, Pseudomonas species selected                    from the group consisting of:                -    Pseudomonas fluorescens, Pseudomonas fluorescens.                    putida and P. chlororaphis, Pseudomonas fluorescens                    VP5, Pseudomonas diazotrophicus, Enterobacter                    cloacae, Trichodema species, Trichoderma virens,                    Trichoderma atroviride strains, Coniothyrium                    minitans, Gliocladium species, Gliocladium virens,                    Gliocladium roseum, and Trichodemw harzianum                    species,            -   (b) one or more nitrification inhibitors selected from                the group consisting of:                2-chloro-6-trichloromethyl)pyridine,                4-amino-1,2,4,6-triazole-HCl,                2,4-diamino-6-trichloromethyltriazine CL-1580,                dicyandiamide (DCD), DCD/formaldehyde reaction products,                methylene bis dicyandiamide, thiourea,                1-mercapto-1,2,4-triazole, ammonium thiosulfate,                dimethylpyrazole organic and inorganic salts, and                2-amino-4-chloro-6-methylpyrimidine,            -   (c) one or more urease inhibitors selected from the                group consisting of: aliphatic phosphoric triamide,                phosphoramides, N-alkyl thiophosphoric triamides            -   (d) and one or more members selected from the group                consisting of pesticide(s), herbicides fungicides(s),                and insecticide(s)    -   b) OPCFs    -   c) one or more members selected from the group consisting of:        -   surfactants, buffers, fragrance/odor masking agents,            colorants, micro-nutrients, and flow modifiers such as            silica.

In one embodiment, the composition of the stable liquid solutionscomprise a) one or more AMP acids and their salts b) one or morenitrification inhibitors and one or more non-AMP acids and their saltsurease inhibitors solubilized within a NOSDS wherein the weight percentcomposition of the NOSDS is 20-99%, the weight percent composition ofthe AMP acids and their salts is 1-80%, the weight percent ofnitrification inhibitors is 0-50% and %, the weight percent of non-AMPacids urease inhibitors is 0-50%. In a variation, These stable liquidsolutions can further comprise one or more members selected from thegroup consisting of: a) surfactants, b) buffers, c) fragrance/odormasking agents, d) colorants, e) micro-nutrients, and f) flow modifiers.

In one embodiment, the NOSDS of the present invention meet one or moreof the following criteria:

-   -   environmentally safe;    -   thermally safe because they have flashpoints above 145° F.;    -   inherently rated safe for contact with humans and animals;    -   able to maintain AMP acids and their salts at levels of 1-80% in        solution to temperatures down to at least 10° C. This ability        means that these compositions have relatively long storage        lives.    -   able to provide improved and even application to fertilizer        granules of inhibitors while not causing clumping of the        granules.    -   They also provide improved stability of urease inhibitors,        primarily alkyl thiophosphoramides such as N-(n-butyl)        thiophosphoric triamide (NBPT) which can be used in combination        with AMP acids and their salts.

In one embodiment, the present invention relates to stable liquidsolutions comprised of a) AMP acids and their salts and b) a Non-aqueousOrganic Solvent Delivery System (NOSDS) wherein AMP acids and theirsalts comprise one or more structures as shown herein.

In an embodiment, the stable liquid solution composition can be furthermodified by addition of additional NOSDS to modify one or moreproperties of the stable liquid solution selected from the groupconsisting of a) viscosity, penetration of a solid surface, adjustinhibitor levels, chill point, dispersibility into a nitrogen source andstorage stability wherein the NOSDS is comprised of one or more membersselected from the group consisting of a) protic and b) aprotic solvents

-   -   wherein one or more protic solvents are selected from the group        consisting: i) an alcohol from the family of C1-10 alkanols, ii)        one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin, iii) poly(C1-10 alkylene) glycols, iv) one or more        alkylene glycols selected from the group consisting of ethylene        glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene        glycol, v) isopropylidene glycerol vi) one or more alkylene        glycol alkyl ethers represented by the structure:

-   -   where R₁ is: CH₃, C₂H₅, C₃H₇ or C₄H₉

-   -   where R₂ is: H or    -   where R₃ is: H or CH₃    -   where R₄ is H and/or CH₃    -   and f is an integer between 1 and 15,    -   vii) one or more alkyl lactates selected from the group        consisting of ethyl, propyl and butyl lactate, viii) one or more        alkanolamines represented by the structure:

-   -   where R₅ is: C₂H₄OR₈ or C₃H₆OH    -   where R₆ is: H, C₂H₄OR₈ or C₃H₆OH    -   where R₇ is: H, C₂H₄OR₈ or C₃H₆OH    -   where R₈ is: (C₂H₄O)_(g)H    -   and g is an integer between 1-10,    -   and ix) glycerol carbonate,    -   and wherein one or more aprotic solvents are selected from the        group consisting of I) dimethyl sulfoxide and/or ii) dialkyl,        diaryl, or alkylaryl sulfoxide(s) having the formula:

R₉S(O)xR₁₀

-   -   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene            group, an aryl group, or C₁₋₃ alkylenearyl group or R₉ and            R₁₀ together with the sulfur to which they are attached form            a 4 to 8 membered ring wherein R₉ and R₁₀ together are a            C₁₋₆ alkylene group which optionally contains one or more            atoms selected from the group consisting of O, S, Se, Te, N,            and P in the ring and x is 1 or 2,

    -   iii) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, iv) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, v) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, vi) isophorone, vii) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, viii) dimethylacetamide, ix)        dimethylformamide, x) dimethyl-2-imidazolidinone, xi)        1-Methyl-2-pyrrolidone, xii) hexamethylphosphoramide, viii)        1,2-dimethyloxyethane, xiv) 2-methoxyethyl ether,        xv)cyclohexylpyrrolidone and xvi) limonene.

In an embodiment, the liquid composition further comprises one or morenitrification inhibitors selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),DCD/formaldehyde reaction products, methylene bis dicyandiamide,thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts, and2-amino-4-chloro-6-methylpyrimidine.

In an embodiment the stable liquid solutions further comprises OPCFsand/or their salts wherein the one or more OPCFs is selected from thegroup consisting of a) organic polymers/oligomers containingpolycarboxylate functionalities and b) amino compounds containingpolycarboxylate functionalities wherein the carboxylic functionalitiesare comprised of one or more members selected from the group consistingof a) carboxylic acids, b) carboxylic anhydrides c) carboxylic imides,d) one or more carboxylic esters and e) carboxylic acid salt whereinsaid salt is derived from the reaction of a neutralizing agent with thecarboxylate function and wherein said carboxylic esters is derived fromthe reaction of said carboxylic function with a protic solvent. In avariation, the neutralizing agents are comprised of one or more metalcations and one or more nitrogen containing compounds wherein the weightpercent of OPFCs is 1-50% of the stable liquid solutions' composition.

In an embodiment, the OPCFs comprise organic polymers/oligomerscontaining polycarboxylate functionalities wherein the composition ofthe polymers/oligomers are one or more members selected from the groupconsisting of a) homopolymers, b) copolymers and c) terpolymers whichare the reaction products of one or more monomer selected from the groupconsisting of aspartic acid, glutamic acid, maleic acid, itaconic acid,citraconic acid, citric acid, acrylic acid and methacrylic acid.

In an embodiment, the OPCFs comprise amino compounds containingpolycarboxylate functionalities wherein the compounds are derived fromone or more amino polycarboxylic acids that are selected from the groupconsisting of ethylenediaminetetraacetic acid,N-hydroxyethylethlyenediaminetriacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,propylenediaminetetraacetic acid, ethylenediamine-N,N′-disuccinic acid,Methylglycinediacetic acid, L-glutamic acid N,N-diacetic acid,nitrilotriacetic acid, N,N bis(carboxymethyl)glutamic acid,Ethylenediamine-N,N-bis(2-hydroxyphenylacetic acid,N,N′-Bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid, Glycine,N,N′-ethylenebis(N-salicyl) and Iminodisuccinic acid.

In an embodiment, said neutralizing agents are comprised of one or moremetal cations and one or more nitrogen containing compounds. In avariation neutralizing agents are comprised of metal cations derivedfrom one or more members selected from the group consisting of a)elemental metals b) metal oxides c) metal hydroxides, d) metal alkylatesand e) metal carbonates and wherein the one or more nitrogen containingcompounds is selected from the group consisting of ammonia, ammoniumhydroxide and organoamines.

In an embodiment, the one or more metal cations' portion of theneutralizing agent is selected from the group consisting of: Na, K, Mg,Ca, Fe, Zn, Mn, Cu, Co, Mo and Ni.

In an embodiment, one or more organoamine neutralizing agents areselected from the group consisting of: a) mono C1-6 amine, b) di C1-6amine, c) tri C1-6 amine, d) monoethanolamine, e) diethanolamine, f)triethanolamine, g) monoisopropylamine, h) diisopropylamine, i)triisopropylamine, j) diethylamine, k) diethylene triamine, l) triethyltetraamine, m) tetraethylpentamine.

In an embodiment, the stable liquid solution can further comprises alkylphosphoramide and alkyl thiophosphoramide. In a variation the alkylthiophosphoramide comprises N-(n-butyl) thiophosphoric triamide.

In an embodiment, the stable liquid solutions and the methods to makethe instant invention are comprised of:

1) preparation of the AMP acids and/or their salts comprises one or moresteps selected from the group consisting of:

-   -   -   a) charge 1 mole of hypophosphorous acid (usually 50%            hypophosphorous acid in water). In a variation, the water is            displaced with a NAPAOL, (non-aqueous polar, aprotic organo            liquid), at 10-40% of the weight of the vessel contents            minus its water content through the use of temperatures of            70-90° C. In another variation, the water is removed through            the use of temperatures of 70-90° C. and by reducing the            pressure of the reaction vessel. In another variation, the            hypophosphorous acid is neutralized to a pH 6.5-10 with one            or more neutralizing agents that are comprised of one or            more members selected from the group consisting of (1) metal            cations derived from one or more members selected from the            group consisting of a) elemental metals b) metal oxides c)            metal hydroxides, d) metal alkylates and e) metal carbonates            wherein the metal cations' portion of the neutralizing agent            is selected from the group consisting of: Na, K, Mg, Ca, Fe,            Zn, Mn, Cu, Co, Mo and Ni, (2) ammonia and (3) ammonium            hydroxide,        -   b) agitate the contents of the reaction vessel and charge            1.8-2.5 moles one or more members selected from the group            consisting of i) paraformaldehyde, ii) formaldehyde and iii)            1,3,5-trioxane maintaining the vessel contents at 25-70 C.            In a variation, vessel content temperature can be controlled            by charge rate. In another variation, the vessel content can            be controlled by using a vessel with a jacket or coils            through which cooling medium can be circulated. In a            variation, the temperature of the vessel content can be            controlled by charge rate and using a using a vessel with a            jacket or coils through which cooling medium can be            circulated After completing step b, maintain temperature of            vessel content at 40-80° C. or at 50-70° C. or at 55-65° C.            for 1 to 8 hours,        -   c) ensure that vessel contents are 25-50° C. and the vessel            contents are clears. In a variation, if vessel composition            contains water, charge a NAPAOL at 10-35% of the weight of            the vessel contents minus its water content and remove the            water by reducing the pressure of the reaction vessel.            Slowly charge to the vessel 0.8-1.2 moles of one or more            reactants selected from the group consisting of i)            ammonia ii) ammonium hydroxide iii) organo amines containing            an aldehyde reactive nitrogen while maintaining temperature            50-80° C. and hold for 1-6 hours until vessel contents            become clear,        -   d) ensure vessel contents are 25-70° C. In a variation a            NAPAOL can be added to the vessel contents at 10-40% of the            weight of the vessel contents minus its water content to            improve fluidity during the water removal step. Slowly            charge to the vessel 0.8-1.2 moles of one or more reactants            selected from the group consisting of i) ammonia ii)            ammonium hydroxide iii) organo amines containing an aldehyde            reactive nitrogen while maintaining temperature 50-80° C.            and hold for 1-6 hours until vessel contents become clear.            In a variation, water is removed from the vessel content by            reducing the pressure in the reaction vessel to assist in            driving the reaction to completion. In another variation,            the pressure reduction to remove water occurs before            charging of 0.8-1.2 of the reactants. In another variation,            the pressure reduction is staged by charging only a portion            of the reactant and allowing the reaction to occur to            prevent loss of the reactant. In another variation, an            acidic catalyst such as methane sulfonic, hypophosphoric or            paratoluene sulfonic acids can be charged to drop pH to            5.0-7.0 to assist in driving the reaction to completion. In            another variation, contents of vessel are heated to            90-110° C. and held 30 minutes, e) reduce the pressure the            reaction vessel until distillation ceases. In a variation,            the reaction vessel pressure is reduced to a pressure            reading of <200 mm Hg. In a variation, the reaction vessel            pressure is reduced to a pressure reading of <100 mm Hg. In            a variation, the reaction vessel pressure is reduced to a            pressure reading of 60-100 mm Hg. In a variation, the            reaction vessel pressure is reduced to a pressure reading of            40-60 mm Hg. In a variation, the reaction vessel pressure is            reduced to a pressure reading of 20-40 mm Hg. In another            variation, the reaction vessel pressure is reduced to a            pressure reading of <20 mmHg,        -   f) vacuum is discontinued when the % moisture is less than            30%. In a variation, vacuum is discontinued when the %            moisture is less than 20%. In a variation, vacuum is            discontinued when the % moisture is less than 10%. In a            variation, vacuum is discontinued when the % moisture is            less than 5%. In another variation, vacuum is discontinued            when the moisture is less than 1%,        -   g) after completion of the reaction, the pH is adjusted to            6-10 with one or more neutralizing agents that are comprised            of one or more members selected from the group consisting            of (1) metal cations derived from one or more members            selected from the group consisting of a) elemental metals b)            metal oxides c) metal hydroxides, d) metal alkylates and e)            metal carbonates wherein the metal cations' portion of the            neutralizing agent is selected from the group consisting of:            Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo and Ni, (2) ammonia            and (3) ammonium hydroxide. In a variation, the pH is            adjusted to 7.5-9.5. In another variation, the pH is            adjusted to 7.5-8.5, and        -   h) the batch is cooled to <40° C.,            wherein a NAPAOL comprises one or more polar, aprotic            solvents selected from the group consisting of: are selected            from the group consisting of i) dimethyl sulfoxide ii)            dialkyl, diaryl, or alkylaryl sulfoxide(s) having the            formula:

R₉S(O)xR₁₀

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃ alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2,    -   iii) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, iv) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, v) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, vi) isophorone, vii) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, viii) dimethylacetamide, ix)        dimethylformamide, x) dimethyl-2-imidazolidinone, xi)        1-Methyl-2-pyrrolidone, xii) hexamethylphosphoramide, viii)        1,2-dimethyloxyethane, xiv) 2-methoxyethyl ether,        xv)cyclohexylpyrrolidone and xvi) limonene.

In an embodiment, AMPs and their salts improve urease inhibition of thetreated urea over untreated urea. In a variation and not to be bound bytheory, AMPs acids and their salts are more hydrolytically and thermallystable versus the traditional phosphoric triamides.

In an embodiment, fertilizer compositions are comprised of a) AMP acidsand their salts and b) nitrogen sources wherein one or more nitrogensources are selected from the group consisting of: urea (molten/solid),manure, compost, urea formaldehyde reaction products (molten/solid),urea/ammonia/formaldehyde reaction products (molten/solid), ammoniumsulfate, anhydrous ammonia, urea/ammonium nitrate aqueous solutions(UAN) and other urea aqueous solutions and

wherein AMP acids and their salts comprise one or more reaction productsof:

-   -   b) one or more phosphorous acids and/or their salts represented        by the following structure:

-   -   -   wherein            -   Z₃ is one or more members selected from the group                consisting of oxygen and sulfur and            -   Z₄ is one or more members selected from the group                consisting of oxygen and sulfur,            -   X₁ is selected from one or more of the group consisting                of selected from the group consisting of:                -   (4) H, Na, Li and K,                -   (5) NH₄,                -   (6) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,

    -   b) one or more aldehydes selected from the group consisting        of i) formaldehyde, ii) paraformaldehyde and iii) 1,3,5-trioxane        and

    -   c) one or more members selected from the group consisting of i)        ammonia ii) ammonium hydroxide iii) one or more organo amines        containing an aldehyde reactive nitrogen selected from the        structure:

-   -   -   wherein R₁₈ is one or more members selected from the group            consisting of: H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,            C₇H₁₅, C₅H₁₂N, C₆H₁₃N₂, C₆H₉N₃, C₆H₇N, C₅H₁₄N₂ and C₈H₁₇,

    -   wherein the resulting composition of the reaction product        contains the following AMPs acid and their salts structures:        -   c.

-   -   -   wherein:            -   i. R₁₁ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅, C₅H₁₂N, C₆H₁₃N₂, C₅H₁₄N₂, C₆H₉N₃, C₆H₇N and                C₈H₁₇,            -   ii. R₁₂ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   iii. R₁₃ is selected from one or more of the group                consisting of H, O—X₃, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                C₆H₁₃, C₇H₁₅, C₈H₁₇, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁,                OC₆H₁₃, OC₇H₁₅ and OC₈H₁₇,            -   iv. X₃ is selected from one or more of the group                consisting of selected from the group consisting of:                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,            -   v. X₁ is selected from one or more of the group                consisting of                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,            -   vi. Z₁ is selected from one or more of the group                consisting of Oxygen and Sulfur,        -   d. and one or more di(aminomethylene)phosphinic acids and            their salts selected from the formula structure:

-   -   -   wherein:            -   i. R₁₄ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅, C₆H₁₃N₂, C₅H₁₄N₂, C₆H₉N₃, C₆H₇N and C₈H₁₇,            -   ii. R₁₅ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   iii. R₁₆ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅ and C₈H₁₇,            -   iv. R₁₇ is selected from one or more of the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   v. X₂ is selected from one or more of the group                consisting of                -   (1) H, Na, Li and K,                -   (2) NH₄,                -   (3) one or more organoamines selected from the group                    consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri                    C₁₋₆ amine, mono ethanol amine, diethanol amine,                    triethanol amine, monoisopropanol amine,                    diisopropanol amine, triisopropanol amine, ethylene                    diamine diethylene triamine, triethylene tetraamine,                    and tetraethylene pentamine,            -   vi. Z₂ is selected from one or more of the group                consisting of Oxygen and Sulfur,            -   vii. Z₆ is selected from one or more of the group                consisting of Oxygen and Sulfur,                wherein the weight composition of the fertilizer                comprises one or more AMP acids and their salts at                0.1-8% and the one or more nitrogen sources at 99.9-92%.

In a variation, the composition of the fertilizer can further compriseNOSDS wherein the composition of the NOSDS is comprised of one or moremembers selected from the group consisting of a) protic and b) aproticsolvents

-   -   wherein one or more protic solvents are selected from the group        consisting: i) an alcohol from the family of C1-10 alkanols, ii)        one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin, iii) poly(C1-10 alkylene) glycols, iv) one or more        alkylene glycols selected from the group consisting of ethylene        glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene        glycol, v) isopropylidene glycerol vi) one or more alkylene        glycol alkyl ethers represented by the structure:

-   -   where R₁ is: CH₃, C₂H₅, C₃H₇ or C₄H₉

-   -   where R₂ is: H or    -   where R₃ is: H or CH₃    -   where R₄ is H and/or CH₃    -   and f is an integer between 1 and 15,    -   vii) one or more alkyl lactates selected from the group        consisting of ethyl, propyl and butyl lactate, viii) one or more        alkanolamines represented by the structure:

-   -   where R₅ is: C₂H₄OR₈ or C₃H₆OH    -   where R₆ is: H, C₂H₄OR₈ or C₃H₆OH    -   where R₇ is: H, C₂H₄OR₈ or C₃H₆OH    -   where R₈ is: (C₂H₄O)_(g)H    -   and g is an integer between 1-10,    -   and ix) glycerol carbonate,    -   and wherein one or more aprotic solvents are selected from the        group consisting of I) dimethyl sulfoxide and/or ii) dialkyl,        diaryl, or alkylaryl sulfoxide(s) having the formula:

R₉S(O)xR₁₀

-   -   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene            group, an aryl group, or C₁₋₃ alkylenearyl group or R₉ and            R₁₀ together with the sulfur to which they are attached form            a 4 to 8 membered ring wherein R₉ and R₁₀ together are a            C₁₋₆ alkylene group which optionally contains one or more            atoms selected from the group consisting of O, S, Se, Te, N,            and P in the ring and x is 1 or 2,

    -   iii) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, iv) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, v) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, vi) isophorone, vii) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, viii) dimethylacetamide, ix)        dimethylformamide, x) dimethyl-2-imidazolidinone, xi)        1-Methyl-2-pyrrolidone, xii) hexamethylphosphoramide, viii)        1,2-dimethyloxyethane, xiv) 2-methoxyethyl ether,        xv)cyclohexylpyrrolidone and xvi) limonene,        wherein the weight composition of the fertilizer comprises one        or more AMP acids and their salts at 0.1-8%, NOSDS at 9.9-2% and        the one or more nitrogen sources at 97.9-90%.

In an embodiment, a method to make a fertilizer composition comprisescharging a) one or more AMPs acids and their salts that is dissolvedinto a NOSDS directly into b) molten urea. In a variation, the AMPs acidand their salts can be dissolved within water and then charged to moltenurea.

In an embodiment, fertilizer compositions are comprised of a) one ormore AMPs acids and their salts) NOSDS, c) nitrogen sources and d) waterwherein one or more nitrogen sources are selected from the groupconsisting of: urea (molten/solid), manure, compost, urea formaldehydereaction products (molten/solid), urea/ammonia/formaldehyde reactionproducts (molten/solid), ammonium sulfate, anhydrous ammonia,urea/ammonium nitrate aqueous solutions (UAN) and other urea aqueoussolutions.

In a variation, said stable liquid solutions can be applied to anitrogen source through a coating or spraying application, added to theurea during the urea production process either in the melt portion ordeposited to the urea during the formation of the urea granule when theurea is still hot, blended into liquefied ammonia gas and added to anaqueous fertilizers such as UAN. In a variation, application levels ofsaid AMPs acids and their salts comprise 0.1-8% of the nitrogen sourcecomposition. In another variation, the NAPAOL comprises 9.9-2% of thefertilizer composition.

In an embodiment, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors dissolved in a Non-aqueous OrganoSolvent Delivery System (NOSDS).

In an embodiment, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors in combination with nitrificationinhibitors by either blending liquid solutions containing each materialor combining the two inhibitors by co-dissolving them together in anon-aqueous organo liquid delivery system (NOSDS).

In an embodiment, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors in combination with other ureaseinhibitors by either blending liquid solutions containing each materialor combining the two inhibitors by co-dissolving them together in anon-aqueous organo liquid delivery system (NOSDS).

In an embodiment, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors in combination with OrganoPolycarboxylate Functionalities, (OPCF), and their salts by eitherblending two separate liquid solutions containing each material orcombining the by dissolving them together in an non-aqueous organoliquid delivery system (NOSDS) formulation.

In an embodiment, the present invention relates to stable liquidsolutions comprising (aminomethylene) phosphinic acids and their saltsutilization as urease inhibitors in combination with nitrificationinhibitors, urease inhibitors and OPCFs and their salts by eitherblending liquid solutions containing each material or combining byco-dissolving them together in a NOSDS. In a variation, the resultingstable liquid solutions can then be applied to fertilizer or to justnitrogen sources to impart inhibiting the conversion of a nitrogensource to ammonia and/or nitrate and freeing soil bound phosphates andmicronutrients.

In an embodiment, stable liquid solutions comprising a) (aminomethylene)phosphinic acids and their salts utilization as urease inhibitors b)Organo Polycarboxylate acid/imide/anhydride c) DCD-formaldehyde reactionproducts and d) NOSDS is applied to fresh manure. Not to be bound bytheory, the better stability of the AMPs acid and their salts to theenvironment associate with fresh manure, the slower migration of theDCD-formaldehyde polymer and the presents of a polyacid results inslower conversion of urea to ammonia, slower conversion of ammonia tonitrates, absorption of ammonia released by the fresh manure by theOPCF-acid/imide/anhydride and the binding of the micronutrientsavailable within the manure by the OPCF resulting in a naturalfertilizer with superior performance in providing the soil and plantsthe needed nutrients for growth.

In an embodiment, the stable liquid solutions are designed to be used inconjunction with a nitrogen source or for direct application to the soilto slow or retard the loss of nitrogen in the soil in order to providenutrients for plant growth.

The following Examples are presented to illustrate certain embodimentsof the present invention.

In an embodiment, the compositions are applied to one or more nitrogensources selected from the group consisting i) urea, ii) urea,formaldehyde reaction products, iii) urea, formaldehyde, and ammoniareaction products, iv) manure, v) dicyandiamide and vi) compost toimpart an increased longevity of plant available nitrogen in the plantgrowth mediums, wherein the compositions comprise one or more ureaseinhibitors dissolved in NOSDS at concentrations of urease inhibitors inthe percent weight ranges of between about 60-95%, 65-95%, 70-95%,75-95%, 80-95%, 85-95%, 60-80%, 65-80%, 70-80%, 75-80%, 60-70%, and65-70% of the compositions. In a variation, nitrogen sources can becoated with high levels of urease inhibitors due to the lower levels oforgano solvents. In another variation, the resulting coated nitrogensources particles can then be mixed with granular natural or syntheticfertilizer or dissolved in water resulting in a liquid fertilizer,wherein when applied to plant growth mediums inhibit the urease enzymeactivities resulting in an extension of plant available nitrogen. In avariation, nitrogen sources coated with high levels of NBPT can be mixedwith other nitrogen sources utilizing the high percent coated nitrogensources as an urease inhibitor deliver vehicle for the other nitrogensources. In one embodiment, it has been found that the compositionsprovides liquid vehicles to deliver even, non-clumping applications ofhigh levels urease inhibitors to the nitrogen sources particles'surfaces with low residual levels of NOSDS. In a variation, high levelsof NOSDS can cause nitrogen sources to become wet and sticky creatingdifficulty in application and negatively impact the physical propertiesof the nitrogen source particles physical properties. These compositionsfor coating nitrogen sources' particles are based on a NOSDS, whichimprove storage life of urease inhibitors such as alkyl thiophosphorictriamides over those formulations containing greater than 1% water.

In an embodiment, the compositions imparts to one or more nitrogensources selected from the group consisting i) urea, ii) urea,formaldehyde reaction products, iii) urea, formaldehyde, and ammoniareaction products, iv) manure, v) dicyandiamide and vi) compost anincreased longevity of plant available nitrogen in the plant growthmediums, wherein the compositions comprise a N-alkyl thiophosphorictriamide dissolved in a non-aqueous organo liquid system atconcentrations of the N-alkyl thiophosphoric triamide in a NOSDS atpercent weight ranges of between about 60-95%, 65-95%, 70-95%, 75-95%,80-95%, 85-95%, 60-80%, 65-80%, 70-80%, 75-80%, 60-70%, and 65-70% ofthe compositions. The resulting coated nitrogen sources particles can beapplied with high levels of alkyl thiophosphoric triamides that can thenbe mixed with natural or synthetic granular fertilizer or dissolved inwater and applied to plant growth mediums imparting the inhibition ofthe enzymatic action of urease slowing the conversion urea nitrogen toammoniacal nitrogen.

In one embodiment, the present invention relates to formulationscomprised of urease inhibitors and a NOSDS and is formulated to coatnitrogen sources particles with an effective level of ureaseinhibitor(s) utilizing moderate temperatures and simple applicationequipment such as spray, meter and controlled flow applicators, mixers,blenders and tumblers

In an embodiment, compositions imparts to one or more nitrogen sourcesselected from the group consisting of i) urea, ii) urea, formaldehydereaction products, iii) urea, formaldehyde, and ammonia reactionproducts, iv) manure, v) dicyandiamide and vi) compost an increasedlongevity of the coated nitrogen sources in plant available nitrogenwithin the plant growth mediums.

In an embodiment, the treated nitrogen sources particles are comprisedof a) one or more nitrogen sources and b) compositions comprised of i)one or more urease inhibitors and ii) a NOSDS, wherein the NOSDS iscomprised of i) dimethyl sulfoxide and optionally ii) one or moresolvents selected from the group consisting of aprotic solvents andprotic solvent(s) wherein said aprotic solvent are one or more membersselected from the group consisting of

-   -   (1) one or more sulfoxide(s) selected from the group consisting        of dialkyl, diaryl, and alkylaryl sulfoxide(s) selected from the        formula

R⁹S(O)xR¹⁰

-   -   -   wherein        -   (a) R⁹ and R¹⁰ are each independently            -   (i) a C₁-C₆ alkylene group, an aryl group or C₁-C₃                alkylenearyl group            -   (ii) with the sulfur to which they are attached form a 4                to 8 membered ring, wherein R⁹ and R¹⁰ together are a                C₁-C₆ alkylene group which optionally contains one or                more atoms selected from the group consisting of O, S,                Se, Te, N, and P in the ring,        -   (b) and x is 1 or 2,

    -   (2) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate,

    -   (3) one or more polyols capped with acetate or formate, wherein        the polyol portion selected from the group consisting of        ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,        butylene glycol, trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol, sorbitan, glucose, fructose,        galactose and glycerin,

    -   (4) one or more alkylene glycol alkyl ethers acetates selected        from the group consisting of dipropylene glycol methyl ether        acetate, tripropylene glycol methyl ether acetate, and        tripropylene glycol butyl ether acetate,

    -   (5) one or more diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate,

    -   (6) one or more alkyl pryrrolidone selected from the group        consisting of 1-Methyl-2-pyrrolidone, butyl pryrrolidone and        cyclohexylpyrrolidone,

    -   (7) one or more members selected from the group consisting of        dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone, isophorone, 1,2-dimethyloxyethane,        2-methoxyethyl ether and limonene,

    -   (8) one or more organo phosphorous liquids selected from the        group consisting of hexamethylphosphoramide and one or more        trialkylphosphates represented by the structure

-   -   -   wherein        -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃,        -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃,        -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃,            and wherein said protic solvent is one or more members            selected from the group consisting of

    -   (1) one or more alcohols selected from the group consisting of        the family of C₁-C₁₀ alkanols,

    -   (2) one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol, sorbitan, glucose, fructose, galactose, and glycerin,

    -   (3) one or more polyalkylene glycols selected from the group        consisting of poly(C₁-C₁₀ alkylene) glycols,

    -   (4) isopropylidene glycerol,

    -   (5) one or more alkylene glycol alkyl ethers represented by the        structure

-   -   -   wherein            -   R¹ is one or more members selected from the group                consisting of CH₃, C₂H₅, C₃H₇ and C₄H₉,            -   R² is one or more members selected from the group                consisting of H                -   and

-   -   -   -   -   wherein                -    R⁴ is one or more members selected from the group                    consisting of H and CH₃,                -    and f is an integer between 1 and 15,

            -   R³ is one or more members selected from the group                consisting of H and CH₃,

    -   (6) one or more alkyl lactates selected from the group        consisting of ethyl lactate, propyl lactate and butyl lactate,

    -   (7) one or more alkanolamines represented by the structure

-   -   -   wherein            -   R⁵ is one or more members selected from the group                consisting of C₂H₄OR⁸ and C₃H₆OH,            -   R⁶ is H, C₂H₄OR⁸ and C₃H₆OH,            -   R⁷ is one or more members selected from the group                consisting of H, C₂H₄OR⁸ and C₃H₆OH,                -   wherein                -    R⁸ is (C₂H₄O)_(g)H, or H,                -    wherein                -    g is an integer between 1-10,

    -   (8) and glycerol carbonate,

    -   wherein the compositions said dry, flowable treated nitrogen        sources comprise between about 0.01-10%, 0.01-8%, 0.01-6%,        0.01-4%, 0.01-3%, 0.01-2%, 0.1-10%, 0.1-8%, 0.1-6%, 0.1-4%,        0.1-2%, 0.1-1%, 0.1-0.75%, 0.1-0.5%, 0.1-0.25%, 0.25-10%,        0.25-5%, 0.25-1%, 0.25-0.75%, 0.5-10%, 0.5-5%, 0.5-2%, 0.5-1%,        0.5-0.75%, 1-10%, 2-10%, 3-10%, 4-10%, 5-10%, 6-10%, 1-5%, and        1-6% of one or more urease inhibitors and between about        0.0011-6.67%, 0.0011-5.33%, 0.0011-4.0%, 0.0011-2.67%,        0.0011-2.0%, 0.0011-1.67%, 0.0011-1.0%, 0.0011-0.5%,        0.0011-0.1%, 0.0011-0.05%, 0.0011-0.011%, 0.011-6.67%,        0.055-6.67%, 0.11-6.67%, 0.22-6.67%, 0.33-6.67%, 0.44-6.67%,        0.55-6.67%, 0.66-6.67%, 0.11-3.33%, and 0.11-4.0% of a NOSDS.

Thus in one embodiment, the present invention relates to compositions ofa solution of urease inhibitor(s) in a NOSDS designed for coating thesurfaces of nitrogen sources, wherein that the NOSDS

-   -   is environmentally safe,    -   has flashpoints above 145° F.,    -   is inherently rated safe for contact with humans and animals,    -   is a liquid solution of urease inhibitors at temperature ranges        of between about −20 to 70° C. comprising a composition        consisting of a percent weight ratio of NOSDS at between about        40-5% to urease inhibitors at between about 60-95%,    -   provides an even and effective coating of urease inhibitors to        the surfaces of nitrogen sources particles while not causing        clumping of the particles.

In one embodiment, the present invention relates to treated nitrogensources having between about 0.01-10% of active urease inhibitor on itssurfaces.

In one embodiment, it has also been discovered that while variousorgano-liquids might meet some of the above criteria, the deliverysystem of the present invention can be optimized to provide aformulation with a high concentration of inhibitors while maintaining achill point range of between about −20° C. to 70° C. by combining two ormore organo-solvents in a solvating delivery system.

In an embodiment, a method of preparing the dry, flowable ureaseinhibitor coated nitrogen sources comprises one or more steps selectedfrom the group consisting of

-   -   a) making compositions of one or more urease inhibitors in a        NOSDS at temperatures ranges of between about 20-70° C., 30-70°        C., 40-70° C., 50-70° C., 60-70° C., 20-60° C., 30-60° C.,        40-60° C., 50-60° C., 20-50° C., 30-50° C., 40-50° C., 20-40°        C., and 30-40° C., wherein the urease inhibitor is in the        percent weight ranges of between about 60-95%, 65-95%, 70-95%,        75-95%, 80-95%, 85-95%, 60-80%, 65-80%, 70-80%, 75-80%, 60-70%,        and 65-70%,    -   b) charging the nitrogen sources particles into a separated        vessel,    -   c) effectuating agitation/mixing of the nitrogen sources        particles in step “b”,    -   d) ensuring the nitrogen sources in step “b” are either at or        are heated to temperature ranges of between about 20-70° C.,        30-70° C., 40-70° C., 50-70° C., 60-70° C., 0-60° C., 30-60° C.,        40-60° C., 50-60° C., 20-50° C., 30-50° C., 40-50° C., 20-40°        C., and 30-40° C.,    -   e) charging slowly the compositions of one or more urease        inhibitors in a NOSDS from step “a” to the nitrogen sources        particles from step “b” while agitating/mixing utilizing one or        more charging method selected from the group consisting of        spray, meter and controlled flow applicators. Alternatively, one        can pour the compositions onto the nitrogen sources if        agitation/mixing are robust enough.    -   f) continuing agitation of materials from step “a” and “d” until        the compositions have uniformly coated the nitrogen sources.

In a variation, the resulting urease inhibitor coated nitrogen sourceswith high levels of the NOSDS, the urease inhibitor coated nitrogensources particles can further comprise a flow modifier in a range ofbetween about 0.25-3.5% of the coated nitrogen sources weight. In avariation, the flow modifiers improve handling properties and particleflow properties of the coated nitrogen sources.

In another variation, the compositions can further comprise a colorant,wherein the colorant composition does not comprise water or alcohol. Ina variation, colorants are dissolved into the compositions or into aNOSDS which is then added to the compositions to enhance visualconformation of the evenness of the coating of nitrogen sources'surfaces.

In an embodiment, the improved delivery compositions have been developedthat can impart effective levels of urease inhibitors to the surface ofnitrogen sources that increase the nitrogen longevity in the plantgrowth mediums. These formulations not only provide a liquid vehicle todeliver an even, non-clumping application of the desired ureaseinhibitors to surfaces of the nitrogen sources particles, but it hasbeen discovered that formulations based on NOSDS improve the storagelife of the important urease inhibitors, such as alkyl thiophosphorictriamides. Alkyl thiophosphoric triamides have been shown to beextremely effective urease inhibitors but suffer from degradation ifexposed to heat and moisture. Thus, in one embodiment, the presentinvention relates to compositions that are substantially free of water.In a variation, substantially free of water is defined as compositionsthat comprise between about 0.05 to 2%, 0.05 to 1%, 0.1 to 2%, 0.2 to2%, 0.5 to 2%, 0.75 to 2%, 1.0 to 2%, 0.05 to 1%, 0.25 to 1%, 0.5 to 1%,and 0.75 to 1% water.

In an embodiment, the compositions of the liquid urease inhibitorsfurther comprises of one or more members selected from the groupconsisting of

-   -   nitrification inhibitors,    -   biologics.    -   additives such as but not limited to surfactants, buffers,        fragrance/odor masking agents, colorants, micro-nutrients, and        flow modifiers such as silica.

In another variation, the compositions can further comprise a colorant,wherein the colorant composition does not comprise water or alcohol. Ina variation, colorants are dissolved into the compositions or into aNOSDS which is then added to the composition to enhance visualconformation of the evenness of the coating of a nitrogen sources'surfaces.

In one embodiment, during the process of coating of the nitrogen sourceswith the liquid urease inhibitors concentrates, one may optionallyinclude one or more members selected from the group consisting ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, and flow modifiers.

In one embodiment, the solvating system of the present invention is aNOSDS, wherein the NOSDS comprises one or more members selected from thegroup consisting of dimethyl sulfoxide, sulfolane, tetramethylsulfoxide, dimethylacetamide, dimethylformamide hexamethylphosphoramide,triethylphosphate, tributyl phosphate, propylene carbonate, ethylenecarbonate, butylene carbonate, N-alkyl-2-pyrrolidone,1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone,ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethyleneglycol, propylene glycol, butylene glycol, trimethylol propane,pentaerythritol, glycerin, trimethylol ethane, triethanolamine,2-(2-aminoethoxy)ethanol, diisopropylamine, triisopropylamine,polyethylene glycol, polypropylene glycol, polyethylene/polypropyleneglycol co-polymer, tripropylene glycol methyl ether, tripropylene glycolbutyl ether, acetate and fumarate capping of glycols which include butare not limited to the following glycols

-   -   ethylene glycol, propylene glycol, butylene glycol, trimethylol        propane, pentaerythritol, glycerin, trimethylol ethane,        polyethylene glycol, polypropylene glycol,        polyethylene/polypropylene glycol co-polymer, Tripropylene        glycol methyl ether, Tripropylene glycol butyl ether.

Additionally, the NOSDS of the compositions further comprises of one ormore members selected from the group consisting of

-   -   a colorant, wherein the colorant composition does not comprise        water or alcohol,    -   scents or masking agents to improve the odor of the        formulations,    -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        nitrogen sources particles, and    -   Buffering agents.

In one embodiment, the dry, flowable coated nitrogen source comprisesurea, wherein the urea is coated with a composition that comprises a)dimethyl sulfoxide (DMSO) and b) NBPT. In a variation, DMSO and NBPT aresources of the micronutrient sulfur and NBPT is also a source ofphosphorous and nitrogen. In one embodiment, the compositions aresubstantially free of water. The process to impart urease inhibitorsonto urea also has cost advantages relative to other systems thatrequire cost prohibitive coating/adhesion technologies or require hightemperatures of molten urea associated with the manufacture of ureagranules and prills.

In one embodiment, the utilization of moderate temperature applicationof compositions onto nitrogen sources particle surfaces allows fornon-clumping of the nitrogen sources particles. In an embodiment, theuse of moderate temperature applications of coatings comprised of NOSDSand one or more urease inhibitors limits the thermal degradationtemperature sensitive urease inhibitors such as the alkyl thiophosphatetriamide, NBPT. In one embodiment, the present invention of coatingnitrogen sources particles with compositions comprising one or moreurease inhibitors allows for the additional benefit of coating utilizingsimple equipment such as blenders, tumbler and mixers. In a variation,the present invention does not require the temperature associated withmolten urea or the cost of the equipment associated with the productionof urea particles.

In an embodiment, the compositions comprises one or more ureaseinhibitors selected from the group consisting of

-   -   a) One or more phosphoramides represented by the structure

-   -   -   wherein            -   R₁₈ is one or more members selected from the group                consisting of CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₆H₅,                C₇H₇, OX₄, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁, OC₆H₁₃,                and HNR₂₁,                -   wherein                -    R₂₁ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and                    C₆H₁₃,                -    X₄ is one or more members selected from the group                    consisting of                -    H, Na, Li, K, NH₄ and one or more organoamines                    selected from the group consisting of mono C₁₋₆                    amine, di C₁₋₆ amine, tri C₁₋₆ amine,                    monoethanolamine, diethanolamine, triethanolamine,                    monoisopropanol amine, diisopropanolamine,                    triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine,            -   R₁₉ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   R₂₀ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   Z₃ is one or more members selected from the group                consisting of oxygen and sulfur.

    -   b) One or more phosphinic acid organo amines and their salts        represented by the structures        -   i)

-   -   -   wherein            -   R₁₁ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅ and C₈H₁₇,            -   R₁₂ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   R₁₃ is one or more members selected from the group                consisting of H, O—X₃, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                C₆H₁₃, C₇H₁₅, C₈H₁₇, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁,                OC₆H₁₃, OC₇H₁₅ and OC₈H₁₇,            -   wherein                -   X₃ is one or more members selected from the group                    consisting of selected from the group consisting of                    H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni, K,                    NH₄, and one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, monoethanol amine, diethanolamine,                    triethanolamine, monoisopropanolamine, diisopropanol                    amine, triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine.                -   X₁ is one or more members selected from the group                    consisting of H, Na, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo,                    Ni, Li, K, NH₄ and one or more organoamines selected                    from the group consisting of mono C₁₋₆ amine, di                    C₁₋₆ amine, tri C₁₋₆ amine, monoethanolamine,                    diethanolamine, triethanolamine,                    monoisopropanolamine, diisopropanolamine,                    triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine,            -   Z₁ is one or more members selected from the group                consisting of oxygen and sulfur, and        -   ii)

-   -   -   wherein            -   R₁₄ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅ and C₈H₁₇            -   R₁₅ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃            -   R₁₆ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃,                C₇H₁₅ and C₈H₁₇                -   R₁₇ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and                    C₆H₁₃                -   X₂ is one or more members selected from the group                    consisting of H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co,                    Mo, Ni, K, NH₄ and one or more organoamines selected                    from the group consisting of mono C₁₋₆ amine, di                    C₁₋₆ amine, tri C₁₋₆ amine, monoethanolamine,                    diethanolamine, triethanolamine,                    monoisopropanolamine, diisopropanolamine,                    triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine.                -   Z₂ is one or more members selected from the group                    consisting of oxygen and sulfur.

In a variation, the compositions comprise the urease inhibitorN-(n-butyl) thiophosphoric triamide.

In one embodiment, the present invention relates to using a moderatetemperature dispersion procedure of between about 20° C.-70° C. with oneor more phosphoramides solubilized into a NOSDS. In one variation, thismoderate temperature procedure and the application of the composition tothe surface of nitrogen sources particles prevents thermal degradationof the phosphoramide, NBPT.

In an embodiment, nitrogen sources particles can be charge to a ribbonblender and warmed to a temperature range of about 30-70° C. Acomposition comprised of a) one or more urease inhibitors, b) colorants,c) fragrances, and d) a NOSDS can be sprayed on the surface of thenitrogen sources while under agitation and mixed until a homogeneouscoating can be observed. Flow aids comprised of one or more membersselected from the group consisting of silicas, nonionic surfactants,soaps, inorganic powders, or nonionic surfactants may be added toimprove the flow of the resulting coated nitrogen sources. In avariation, the temperature of compositions comprising of the NOSDS andone or more urease inhibitors can be heated to 70° C. with minimaldegradation of temperature sensitive urease inhibitors such as NBPT.

In an embodiment, the dry, flowable coated nitrogen sources can beapplied to plant growth mediums as aqueous liquids and/or as nitrogensources particle forms to provide improved nitrogen retention in theplant growth mediums for uptake by plant life.

In an embodiment, the dry, flowable coated nitrogen sources furthercomprises water, wherein an aqueous nitrogen sources solution can beadded directly to the plant growth mediums or blended one or morefertilizer components selected from the group consisting of mono anddiammonium phosphate, ammonium nitrate, ammonium sulfate, micronutrientsalts such as Calcium sulfate and zinc sulfate, chelated micronutrientssuch as FeEDDHA, ZnEDTA and Polyorgano acids and their salts.

In an embodiment, the dry, flowable coated nitrogen sources comprisecoating on the surface of a) one or more nitrogen sources selected fromthe group consisting of i) urea, ii) urea, formaldehyde reactionproducts, iii) urea, formaldehyde, and ammonia reaction products, iv)manure, v) dicyandiamide and vi) compost, wherein the coating iscompositions comprised of a) a NOSDS and b) one or more ureaseinhibitors selected from the group consisting of i) one or morephosphoramides selected from the group consisting of (a) phosphorictriamides, (b) thiophosphoric triamides, (c) alkyl thiophosphorictriamides, wherein the alkyl thiophosphoric triamides has one or morealkyl groups that independently contain between 1 and 6 carbon atoms,and ii) one or more phosphinic acid organo amines selected from thegroup consisting of (a) bis(aminomethyl)phosphinic acids, (b)aminomethyl(alkylaminomethyl)phosphinic acids, and (c)di(alkylaminomethy)phosphinic acids, wherein the compositions ofphosphinic acids comprise phosphinic acids salts.

In an embodiment, the composition may further comprise one or moremembers selected from the group consisting of surfactants, buffers,fragrance/odor masking agents, colorants, micro-nutrients, and flowmodifiers, wherein the one or more member do not comprise water oralcohol.

In another variation, the compositions may further comprise a colorant,wherein the colorant composition does not comprise water or alcohol. Ina variation, colorants are dissolved into the liquid composition or intoa NOSDS which is then added to the liquid composition to enhance visualconformation of the evenness of the coating of nitrogen sourcessurfaces.

In an embodiment, the composition is substantially free of water.

In one embodiment, the compositions are comprised of NBPT and a NOSDSand are formulated to coat nitrogen sources particles with an effectivelevel of NBPT utilizing simple application equipment such as mixers,blenders and tumblers.

In an embodiment, the NOSDS is comprised of one or more non-aqueousorgano solvents selected from the group consisting of a) aproticsolvents and b) protic solvents, wherein said protic solvents areselected from the group consisting of i) an alcohol from the family ofC₁₋₁₀ alkanols, ii) one or more polyols selected from the groupconsisting of trimethylol propane, trimethylol ethane, pentaerythritol,sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, iii)poly(C1-10 alkylene) glycols, iv) one or more alkylene glycols selectedfrom the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2propylene glycol, and butylene glycol, v) isopropylidene glycerol vi)one or more alkylene glycol alkyl ethers represented by the structure

-   -   wherein        -   R¹ is CH₃, C₂H₅, C₃H₇ or C₄H₉        -   R² is H or

-   -   -   R³ is H or CH₃,            -   wherein                -   R⁴ is H or CH₃,                -   and f is an integer between 1 and 15,

    -   vii) one or more alkyl lactates selected from the group        consisting of ethyl lactate, propyl lactate and butyl        lactate, viii) one or more alkanolamines represented by the        structure

-   -   wherein        -   R⁵ is C₂H₄OR⁸ or C₃H₆OH,        -   R⁶ is H, C₂H₄OR⁸ or C₃H₆OH,        -   R⁷ is H, C₂H₄OR⁸ or C₃H₆OH,            -   R⁸ is (C₂H₄O)_(g)H or H,            -   and g is an integer between 1 and 10,    -   ix) and glycerol carbonate, and wherein said aprotic solvents        are selected from the group consisting of i) dimethyl        sulfoxide, ii) dialkyl, diaryl, and alkylaryl sulfoxide(s)        having the formula

R⁹S(O)xR¹⁰

-   -   wherein        -   R⁹ and R¹⁰ are each independently a C₁₋₆ alkylene group, an            aryl group, or C₁₋₃ alkylenearyl group or R⁹ and R¹⁰ with            the sulfur to which they are attached form a 4 to 8 membered            ring, wherein R⁹ and R¹⁰ together are a C₁₋₆ alkylene group            which optionally contains one or more atoms selected from            the group consisting of O, S, Se, Te, N, and P in the ring            and x is 1 or 2,    -   iii) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, iv) one or more polyols capped with acetate        or formate, wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol, sorbitan,        glucose, fructose, galactose and glycerin, v) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate, vi) isophorone, vii) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, viii) dimethylacetamide, ix)        dimethylformamide, x) dimethyl-2-imidazolidinone, xi) one or        more alkyl pyrrolidones selected from the group consisting of        1-Methyl-2-pyrrolidone and butyl pyrrolidone, xii) one or more        organo phosphorous liquids selected from the group consisting of        hexamethylphosphoramide and one or more trialkylphosphates        represented by the structure

-   -   -   wherein            -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃,            -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃,            -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃,

    -   xiii) 1,2-dimethyloxyethane, xiv) 2-methoxyethyl ether,        xv)cyclohexylpyrrolidone and xvi) limonene.

In a variation, the composition imparts to one or more nitrogen sourcesselected from the group consisting of i) urea, ii) urea, formaldehydereaction products, iii) urea, formaldehyde, and ammonia reactionproducts, iv) manure, v) dicyandiamide and vi) compost an increasedlongevity of plant available nitrogen, wherein the coated nitrogensources are dry, flowable particles comprising i) one or more nitrogensources and ii) compositions comprised of (a) one or more ureaseinhibitors and (b) a NOSDS, wherein the NOSDS is comprised of one ormore aprotic solvents selected from the group consisting of 1) dimethylsulfoxide, 2) dialkyl, diaryl, and alkylaryl sulfoxide(s) having theformula

R⁹S(O)xR¹⁰

-   -   -   wherein            -   R⁹ and R¹⁰ are each independently a C₁₋₆ alkylene group,                an aryl group, or C¹⁻³ alkylenearyl group or R⁹ and R¹⁰                with the sulfur to which they are attached form a 4 to 8                membered ring, wherein R⁹ and R¹⁰ together are a C                alkylene group which optionally contains one or more                atoms selected from the group consisting of O, S, Se,                Te, N, and P in the ring and x is 1 or 2                wherein such that the compositions' weight percents are                83.33-99.99% nitrogen sources, 10-0.011% urease                inhibitors and 6.67-0.0011% NOSDS.

In a variation, the NOSDS comprises DMSO

In one embodiment, the compositions of the present invention relates tocompositions of NBPT and a NOSDS and that is designed to coat nitrogensources particles with an effective level of NBPT utilizing simpleapplication equipment such as mixers, blenders and tumblers. In anembodiment, the NOSDS is comprised of one or more solvents selected fromthe group consisting of

-   -   dimethyl sulfoxide, sulfolane, tetramethyl sulfoxide,        dimethylacetamide, dimethylformamide, hexamethylphosphoramide,        triethylphosphate, tributylphophate, propylene carbonate,        ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone,        1,2-dimethyloxyethane, 2-methoxyethyl ether,        cyclohexylpyrrolidone, ethyl lactate, 1,3        dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene        glycol, butylene glycol, trimethylol propane, pentaerythritol,        glycerin, trimethylol ethane, triethanolamine,        2-(2-aminoethoxy)ethanol, diisopropylamine, triisopropylamine,        polyethylene glycol, polypropylene glycol,        polyethylene/polypropylene glycol co-polymer, tripropylene        glycol methyl ether, tripropylene glycol butyl ether,        acetate/fumarate capping of glycols which include but are not        limited to the following glycols ethylene glycol, propylene        glycol, butylene glycol, trimethylol propane, pentaerythritol,        glycerin, trimethylol ethane, polyethylene glycol, polypropylene        glycol, polyethylene/polypropylene glycol co-polymer,        tripropylene glycol methyl ether, and tripropylene glycol butyl        ether.

In an embodiment, the present invention comprises nitrogen sourcescoated with concentrated liquid additives. In one embodiment, theconcentrated liquid additives comprise one or more urease inhibitorsdispersed in a NOSDS.

In an embodiment, the concentrated liquid additives comprise one or moreurease inhibitors selected from the group consisting of a) one or morephosphoramides selected from the group consisting of i) phosphorictriamides, ii) thiophosphoric triamides, iii) alkyl thiophosphorictriamides, wherein the alkyl thiophosphoric triamides has one or morealkyl groups that independently contain between 1 and 6 carbon atoms,and b) one or more phosphinic acid organo amines selected from the groupconsisting of i) bis(aminomethyl)phosphinic acids, ii)aminomethyl(alkylaminomethyl)phosphinic acids, and iii)di(alkylaminomethy)phosphinic acids, wherein converting the phosphinicacids to their salts is optional.

In an embodiment, the methods of making the urease inhibitorcompositions for coating nitrogen sources comprises one or more stepsselected from the group consisting of

-   -   1) heating a composition comprising a NOSDS and one or more        urease inhibitors that are selected from the group consisting        of a) one or more phosphoramides selected from the group        consisting of i) phosphoric triamides, ii) thiophosphoric        triamides, ii) alkyl thiophosphoric triamides, wherein the alkyl        thiophosphoric triamides has one or more alkyl groups that        independently contain between 1 and 6 carbon atoms, b) one or        more phosphinic acid organo amines selected from the group        consisting of i) bis(aminomethyl)phosphinic acids, ii)        aminomethyl(alkylaminomethyl)phosphinic acids, and iii)        di(alkylaminomethy)phosphinic acids, wherein the phosphinic        acids salts are optional, to temperature ranges of between about        20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70° C., 20-60°        C., 30-60° C., 40-60° C., 50-60° C., 20-50° C., 30-50° C.,        40-50° C., 20-40° C., and 30-40° C., and wherein the urease        inhibitors are in the % weight ranges of between about 60-95%,        65-95%, 70-95%, 75-95%, 80-95%, 85-95%, 60-80%, 65-80%, 70-80%,        75-80%, 60-70%, and 65-70% of said composition,    -   2) effectuate mixing of the composition,    -   3) holding the mixture to a temperature that the composition is        fluid and that, optionally, allows addition of one or more        members selected from the group consisting of surfactants,        buffers, fragrance/odor masking agents, non-water and        non-alcohol containing colorants, micro-nutrients, and flow        modifiers.

In an embodiment, a method of preparing the urease inhibitor coatednitrogen sources comprise one or more steps selected from the groupconsisting of

-   -   a) maintain said composition liquid at temperatures ranges of        between about 20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70°        C., 20-60° C., 30-60° C., 40-60° C., 50-60° C., 20-50° C.,        30-50° C., 40-50° C., 20-40° C.,    -   b) charge nitrogen sources particles to a separate vessel,    -   c) effectuate mixing of the nitrogen sources,    -   d) ensure the nitrogen sources in either at or are heated to        temperature ranges of between about 20-70° C., 30-70° C., 40-70°        C., 50-70° C., 60-70° C., 20-60° C., 30-60° C., 40-60° C.,        50-60° C., 20-50° C., 30-50° C., 40-50° C., 20-40° C., and        30-40° C.,    -   e) charge slowly said compositions from step “a” to nitrogen        sources particles in step “d” while continuing to effectuate        agitation,    -   f) continue to effectuate mixing of nitrogen sources until the        composition has uniformly coated the nitrogen sources,    -   g) cool the urease inhibitor coated nitrogen sources to        temperatures ranges of between about 0-60° C., 20-50° C., 30-50°        C., 40-50° C., 20-40° C., 30-40° C., 10-50° C., 10    -   40° C., 10-30° C., 10-20° C., 0-50° C., 0-40° C., 10-30° C.,        10-20° C.    -   h) add a flow modifier to improve handling and flow properties,        and wherein the coated nitrogen sources are dry, flowable        particles.

In a variation, the flow modifier is a hydrophobized silica.

In another variation, the compositions can further comprise a colorant,wherein the colorant composition does not comprise water or alcohol. Ina variation, colorants are dissolved into the composition or into aNOSDS which is then added to the composition to enhance visualconformation of the evenness of the coating of nitrogen sources'surfaces. In an embodiment, the method comprises further adding thecompositions to coat nitrogen sources utilizing simple blendingequipment.

In one variation, the dry, flowable urease inhibitor coated nitrogensources comprises one or more nitrogen sources selected from the groupconsisting of i) urea, ii) urea, formaldehyde reaction products, iii)urea, formaldehyde, and ammonia reaction products, iv) manure, v)dicyandiamide and vi) compost.

In one embodiment, the concentrated liquid concentrates comprisecompositions that are substantially free of water.

In an embodiment, composition comprising of nitrogen sources coated withurease inhibitors that have been solubilized with a NOSDS such that thecompositions' weight percents are 83.33-99.99% nitrogen sources,10-0.011% urease inhibitors and 6.67-0.0011% NOSDS. In one variation,the NOSDS is dimethyl sulfoxide. In another variation, the nitrogensources comprise urea. In another variation, the urease inhibitorcomprises NBPT.

In an embodiment, a composition is charged during the cooling step ofthe nitrogen sources particles formation processes, wherein the nitrogensources particle forming processes comprise one or more processesselected from the group consisting of a) rotating drum granulation, b)fluidized bed granulation, and c) pilling tower.

In an embodiment, a method of making urease inhibitor coated nitrogensources in the rotating drum process comprises one or more stepsselected from the group consisting of

-   -   a) achieving the desired nitrogen sources particle size at the        end of the particle forming process,    -   b) terminating the spraying of molten nitrogen sources onto a        bed of small nitrogen sources particles (nitrogen sources        particle seed),    -   c) spraying the composition onto the nitrogen sources particles        during the process, wherein the continued application of layers        of molten nitrogen sources are being sprayed upon the nitrogen        sources in the rotating drum bed, wherein the air flow and        temperature are optimized to ensure limited exposure of        composition to temperature ranges of between about 80-100° C.    -   d) achieving the temperature range of the nitrogen sources is        between about 20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70°        C., 20-60° C., 30-60° C., 40-60° C., 50-60° C., 20-50° C.,        30-50° C., 40-50° C., 20-40° C., and 30-40° C.,    -   e) spraying the composition that are at temperature ranges of        between about 20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70°        C., 20-60° C., 30-60° C., 40-60° C., 50-60° C., 20-50° C.,        30-50° C., 40-50° C., 20-40° C., and 30-40° C. onto the nitrogen        sources particles while the nitrogen sources are mixed within        the rotating drum,    -   f) achieving an even coating of the composition on the surfaces        of the nitrogen sources,    -   g) cooling the coated nitrogen sources to desired packaging        temperatures,    -   h) adding one or more flow modifiers to improve the handling and        flow properties of the urease inhibitor coated nitrogen sources,    -   i) storing or packaging the resulting urease inhibitor coated        nitrogen sources.

In an embodiment, a method of making urease inhibitor coated nitrogensources in the fluidized bed granulation process comprises one or moresteps selected from the group consisting of

-   -   a) achieving the desired nitrogen sources particle size at the        end of the particle forming process,    -   b) terminating the spraying of molten nitrogen sources onto a        bed of small nitrogen sources particles (nitrogen sources        particle seed),    -   c) spraying the composition onto the nitrogen sources particles        during the process, wherein the continued application of layers        of molten nitrogen sources are being sprayed upon the nitrogen        sources on the fluidized bed, wherein the air flow and        temperature are optimized to ensure limited exposure of        compositions to temperatures of between about 80-100° C.,    -   d) achieving the temperature range of the nitrogen sources is        between about 20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70°        C., 20-60° C., 30-60° C., 40-60° C., 50-60° C., 20-50° C.,        30-50° C., 40-50° C., 20-40° C., and 30-40° C.,    -   e) spraying the compositions that are at temperature ranges of        between about 20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70°        C., 20-60° C., 30-60° C., 40-60° C., 50-60° C., 20-50° C.,        30-50° C., 40-50° C., 20-40° C., and 30-40° C. onto the nitrogen        sources particles while the nitrogen sources are mixed by forced        air passing over the nitrogen sources particles on the fluidized        bed,    -   f) achieving an even coating of the compositions on the surfaces        of the nitrogen sources,    -   g) cooling the coated nitrogen sources to desired packaging        temperatures, h) adding one or more flow modifiers to improve        the handling and flow properties of the urease inhibitor coated        nitrogen sources,    -   i) storing or packaging the resulting urease coated nitrogen        sources.

In an embodiment, a method of making urease inhibitor coated nitrogensources in the prilling tower processes comprises one or more stepsselected from the group consisting of

-   -   a) forming droplets of the molten nitrogen sources as they pass        through the shower head into the tower,    -   b) flowing counter current air up the tower cooling the droplets        below the nitrogen sources freezing point forming small, round,        solid pellets called prills,    -   c) spraying the composition onto the nitrogen sources droplets        before crystallizing, wherein the counter current air flow and        temperature are optimized to ensure limited exposure of        composition to temperatures of between about 80-100° C.,    -   d) achieving the temperature range of the nitrogen sources        prills is between about 20    -   70° C., 30-70° C., 40-70° C., 50-70° C., 60-70° C., 20-60° C.,        30-60° C., 40-60° C., 50-60° C., 20-50° C., 30-50° C., 40-50°        C., 20-40° C., and 30-40° C.,    -   e) spraying the compositions that are at temperature ranges of        between about 20-70° C., 30-70° C., 40-70° C., 50-70° C., 60-70°        C., 20-60° C., 30-60° C., 40-60° C., 50-60° C., 20-50° C.,        30-50° C., 40-50° C., 20-40° C., and 30-40° C. onto the nitrogen        sources particles while the nitrogen sources are mixed by the        counter current air flowing up the tower,    -   f) achieving an even coating of the composition on the surfaces        of the nitrogen sources,    -   g) cooling the coated nitrogen sources to desired packaging        temperatures,    -   h) adding one or more flow modifiers to improve the handling and        flow properties of the urease inhibitor coated nitrogen sources        at the bottom of the tower,    -   i) storing or packaging the resulting urease inhibitor coated        nitrogen sources.

In an embodiment, the levels of urease inhibitors in plant growthmediums necessary to provide effective urease inhibition to extend thelongevity of plant available nitrogen in the plant growth mediums is atleast 0.02 ppm. In a variation, the necessary level of urease inhibitorsin plant growth medium is 0.02-5000, 0.02-4000 ppm, ppm, 0.02-3000 ppm,0.02-2000 ppm, 0.02-1000 ppm, 0.1-5000 ppm, 0.1-4000 ppm, 0.1-3000 ppm,0.1-2000 ppm, 0.1-1000 ppm, 1.0-5000 ppm, 1.0-4000 ppm, 1.0-3000 ppm,1.0-2000 ppm, 1.0-1000 ppm, 5.0-5000 ppm, 5.0-4000 ppm, 5.0-3000 ppm,5.0-2000 ppm, 5.0-1000 ppm, 5.0-500 ppm, 5.0-400 ppm, 5.0-300 ppm,5.0-200 ppm, and 5-100 ppm to provide effective urease inhibition. In avariation, the effective level of urease inhibitors is delivered by thedry, flowable urease inhibitor coated nitrogen sources particles. Inanother variation, the effective levels of urease inhibition aredelivered by application of said coated nitrogen sources particlesdirectly to plant growth mediums or through a dissolution into water andapplied to plant growth mediums as part of a liquid fertilizer.

In an embodiment, compositions that impart to one or more nitrogensources selected from the group consisting of i) urea, ii) urea,formaldehyde reaction products, iii) urea, formaldehyde, and ammoniareaction products, iv) manure, v) dicyandiamide and vi) compost anincreased longevity of plant available nitrogen in the plant growthmediums, wherein the urease coated urea is dry, flowable particlescoated with a composition comprising of one or more urease inhibitorsthat have been solubilized within a NOSDS. In an embodiment, the NOSDSis comprised of one or more aprotic organo solvents are selected fromthe group consisting of

-   -   a) dimethyl sulfoxide and    -   b) one or more sulfoxide(s) selected from the group consisting        of dialkyl, diaryl, and alkylaryl sulfoxide(s) selected from the        formula

R⁹S(O)xR¹⁰

-   -   -   wherein            -   R⁹ and R¹⁰ are each independently a C₁-C₆ alkylene                group, an aryl group or C₁-C₃ alkylenearyl group or R⁹                and R¹⁰ with the sulfur to which they are attached form                a 4 to 8 membered ring, wherein R⁹ and R¹⁰ together are                a C₁-C₆ alkylene group which optionally contains one or                more atoms selected from the group consisting of O, S,                Se, Te, N, and P in the ring and x is 1 or 2

    -   wherein the NOSDS optional further comprised of aprotic and        protic solvents, wherein the aprotic solvents are one or more        members selected from the group consisting of

    -   a) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate

    -   b) one or more polyols capped with acetate or formate, wherein        the polyol portion is selected from the group consisting of        ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,        butylene glycol, trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol, sorbitan, glucose, fructose,        galactose and glycerin

    -   c) one or more alkylene glycol alkyl ethers acetates selected        from the group consisting of dipropylene glycol methyl ether        acetate, tripropylene glycol methyl ether acetate, and        tripropylene glycol butyl ether acetate,

    -   d) one or more diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate,

    -   e) one or more alkyl pryrrolidone selected from the group        consisting of 1-Methyl-2-pyrrolidone and cyclohexylpyrrolidone,

    -   f) one or more members selected from the group consisting of        dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone, isophorone, 1,2-dimethyloxyethane,        2-methoxyethyl ether and limonene

    -   g) one or more organo phosphorous liquids selected from the        group consisting of hexamethylphosphoramide and one or more        trialkylphosphates represented by the structure

-   -   -   wherein            -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃,            -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃,            -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃,                and wherein one or more protic solvent are selected from                the group consisting of

    -   a) one or more alcohols selected from the group consisting of        the family of C₁-C₁₀ alkanols

    -   b) one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol, sorbitan, glucose, fructose, galactose, and glycerin

    -   c) one or more polyalkylene glycols selected from the group        consisting of poly(C₁-C₁₀ alkylene) glycols,

    -   d) isopropylidene glycerol

    -   e) one or more alkylene glycol alkyl ethers represented by the        structure

-   -   -   wherein            -   R¹ is one or more members selected from the group                consisting of CH₃, C₂H₅, C₃H₇ and C₄H₉,            -   R² is one or more members selected from the group                -   consisting of H and

-   -   -   -   wherein                -   where R⁴ is one or more members selected from the                    group consisting of H and CH₃,                -   and f is an integer between 1 and 15,            -   wherein R³ is one or more members selected from the                group consisting of H and CH₃,

    -   f) one or more alkyl lactates selected from the group consisting        of ethyl lactate, propyl lactate and butyl lactate,

    -   g) one or more alkanolamines represented by the structure

-   -   -   wherein            -   R⁵ is one or more members selected from the group                consisting of C₂H₄OR⁸ and C₃H₆OH,            -   R⁶ is H, C₂H₄OR⁸ and C₃H₆OH,            -   R⁷ is one or more members selected from the group                consisting of H, C₂H₄OR⁸ and C₃H₆OH,                -   wherein                -    R⁸ is (C₂H₄O)_(g)H or H,                -    wherein                -    g is an integer between 1-10

    -   h) and glycerol carbonate,        and wherein the resulting dry, flowable urease inhibitor coated        nitrogen sources compositions' weight percents are 83.33-99.99%        nitrogen sources, 10-0.011% urease inhibitors and 6.67-0.0011%        NOSDS.

In a variation, the nitrogen sources comprise urea.

In a variation, the NOSDS comprises DMSO and one or more solventsselected from the group consisting of protic and aprotic solvents,wherein the weight ratio of urease inhibitors to NOSDS comprise betweenabout 60-40%, 65-35%, 70-30%, 75-25%, 80-20%, 85-15%, and 95-5% of thecompositions.

In an embodiment, compositions comprise one or more urease inhibitorsselected from the group consisting of

-   -   a) one or more phosphoramide represented by the structure

-   -   -   wherein            -   R₁₈ is one or more members selected from the group                consisting of CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₆H₅,                C₇H₇, OX₄, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉, OC₅H₁₁, OC₆H₁₃,                and HNR₂₁,                -   wherein                -    R₂₁ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and                    C₆H₁₃,                -    X₄ is one or more members selected from the group                    consisting of H, Na, Li, K, NH₄ and one or more                    organoamines selected from the group consisting of                    mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆ amine,                    monoethanolamine, diethanolamine, triethanolamine,                    monoisopropanolamine, diisopropanolamine,                    triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine,            -   R₁₉ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   R₂₀ is one or more members selected from the group                consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and C₆H₁₃,            -   Z₃ is one or more members selected from the group                consisting of oxygen and sulfur,

    -   b) one or more phosphinic acids organo amines and their salts        represented by the structures        -   i)

-   -   -   -   wherein                -   R₁₁ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                    C₆H₁₃, C₇H₁₅ and C₈H₁₇,                -   R₁₂ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and                    C₆H₁₃,                -   R₁₃ is one or more members selected from the group                    consisting of H, O—X₃, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                    C₆H₁₃, C₇H₁₅, C₈H₁₇, OCH₃, OC₂H₅, OC₃H₇, OC₄H₉,                    OC₅H₁₁, OC₆H₁₃, OC₇H₁₅ and OC₈H₁₇,                -   wherein                -    X₃ is one or more members selected from the group                    consisting of selected from the group consisting of                    H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, Ni, K,                    NH₄ and one or more organoamines selected from the                    group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,                    tri C₁₋₆ amine, monoethanol amine, diethanolamine,                    triethanolamine, monoisopropanolamine,                    diisopropanolamine, triisopropanolamine,                    ethylenediamine diethylenetriamine,                    triethylenetetraamine, and tetraethylenepentamine,                -   X₁ is one or more members selected from the group                    consisting of H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co,                    Mo, Ni, K, NH₄ and one or more organoamines selected                    from the group consisting of mono C₁₋₆ amine, di                    C₁₋₆ amine, tri C₁₋₆ amine, monoethanolamine,                    diethanolamine, triethanolamine,                    monoisopropanolamine, diisopropanolamine,                    triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine,                -   Z₁ is one or more members selected from the group                    consisting of oxygen and sulfur, and

        -   ii)

-   -   -   -   wherein                -   R₁₄ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                    C₆H₁₃, C₇H₁₅ and C₈H₁₇,                -   R₁₅ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, and                    C₆H₁₃,                -   R₁₆ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁,                    C₆H₁₃, C₇H₁₅ and C₈H₁₇,                -   R₁₇ is one or more members selected from the group                    consisting of H, CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁ and                    C₆H₁₃,                -   X₂ is one or more members selected from the group                    consisting of H, Na, Li, Mg, Ca, Fe, Zn, Mn, Cu, Co,                    Mo, Ni, K, NH₄ and one or more organoamines selected                    from the group consisting of mono C₁₋₆ amine, di                    C₁₋₆ amine, tri C₁₋₆ amine, monoethanolamine,                    diethanolamine, triethanolamine,                    monoisopropanolamine, diisopropanolamine,                    triisopropanolamine, ethylenediamine                    diethylenetriamine, triethylenetetraamine, and                    tetraethylenepentamine,                -   Z₂ is one or more members selected from the group                    consisting of oxygen and sulfur.

In a variation, the compositions comprise one or more urease inhibitorsselected from the group consisting of N-(n-butyl) thiophosphorictriamide and, aminomethyl(hexylaminomethyl)phosphinic acid (C₈H₂₁N₂O₂P)and its salts, wherein said salt is derived from the reaction of aneutralizing agents with the phosphinic acid, and wherein saidneutralizing agents are comprised of a) one or more metal cations,wherein metal cations are derived from one or more members selected fromthe group consisting of i) elemental metals ii) metal oxides iii) metalhydroxides, iv) metal alkylates and v) metal carbonates, wherein the oneor more metal cations' portion of the neutralizing agent is selectedfrom the group consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo andNi.

In a variation, the compositions comprise the urease inhibitorN-(n-butyl) thiophosphoric triamide.

In another variation, the urease inhibitors comprise phosphinic acidsorgano amines and their salts, wherein the one or more of the phosphinicacid organo amines are selected from the group consisting ofaminomethyl(N-n-hexylaminomethyl)phosphinic acid,aminomethyl(methylaminomethyl)phosphinic acid,aminomethyl-(N-n-ethylaminomethyl)phosphinic acid,aminomethyl(N-n-propylaminomethyl)phosphinic acid,aminomethyl(N-n-butylaminomethyl)phosphinic acid, aminomethyl(isobutylaminomethyl)phosphinic acid, aminomethyl(N-n-pentylaminomethyl)phosphinic acid,aminomethyl(N-n-heptylaminomethyl)phosphinic acid,aminomethyl(N-n-octylaminomethyl)phosphinic acid,aminomethyl(benzylaminomethyl)phosphinic acid,Bis(aminomethyl)phosphinic acid, Bis(methylaminomethyl)phosphinic acid,Bis(N-n-ethylaminomethyl)phosphinic acid,Bis(N-n-propylaminomethyl)phosphinic acid,Bis(N-n-hexylaminomethyl)phosphinic acid,methylaminomethyl(N-n-hexylaminomethyl)phosphinic acid,ethylaminomethyl(N-n-hexylaminomethyl)phosphinic acid,propylaminomethyl(N-n-hexylaminomethyl)phosphinic acid, andbutylaminomethyl(N-n-hexylaminomethyl)phosphinic acid.

In an embodiment, the compositions are comprised of urease inhibitorsthat are in a solution within the NOSDS at a weight ratio of betweenabout 60-95% urease inhibitors to between about 40-5% of a NOSDS.

In an embodiment, the compositions further comprise one or morebiologics selected from the group consisting of

-   -   a) one or more biologics selected from the group consisting of        -   i)Bacillus biologics, ii) Azospirillum biologics, iii)            Azobacter biologics iv) Gluconacetobacter biologics, v)            Phosphobacteria, vi) Cyanobacteria, vii)            Herbaspirillum, viii) Burkholderia, ix) Pseudomonas, x)            Gluconacetobacter, xi) Enterobacter, xii) Klebsiella, xiii)            Burkholderia, xiv) Bradyrhiwbium species, xv) Bradyrhiwbium            japonicum, xvi) Rhizobium meliloti, xvii) Laccaria            bicolor, xviii) Glomus imraradices timanita, xix)            Actinomyces, xx) Penicillium, xxi) Mesorhizobiwn            cicero, xxii) one or more insecticidal or insect repellent            microbial species and strains are selected from the group            consisting of            -   Telenomus podisi, Baculovirus anticarsia, Trichogramma                pretiosum, Trichogramma gallai, Chromobacterium                subtsugae, Trichoderma fertile, Beauveria bassiana,                Beauveria bassiana, Beauveria bassiana, Paecilomyces                jknwsoroseu, Trichoderma harzianum, Verticillium                lecanii, lsarfofumosarosea Lecanicillium muscarium,                Streptomyces microflavus, and Muscodor albus,        -   xxiii) one or more nematodal microbial species and strains            are selected from the group consisting of            -   Myrothecium verrucaria, Pasteuria species, Pasteuria                Metarhizium species, and Flavobacteriwn species        -   xxiv) Reynoutria sachalinensis and        -   xxv) one or more antifungal, antimicrobial and plant growth            promoting microbial species and strains are selected from            the group consisting of Gliocladium species, Pseudomonas            species selected from the group consisting of            -   Pseudomonas fluorescens, Pseudomonas fluorescens. putida                and P. chlororaphis, Pseudomonas fluorescens VP5,                Pseudomonas diazotrophicus, Enterobacter cloacae,                Trichodema species, Trichoderma virens, Trichoderma                atroviride strains, Coniothyrium minitans, Gliocladium                species, Gliocladium virens, Gliocladium roseum, and                Trichodemw harzianum species,

In an embodiment, the composition further comprises surfactants,buffers, fragrance/odor masking agents, colorants, micro-nutrients,dispersed nitrification inhibitors and flow modifiers, wherein thecomposition does not comprise water and alcohol.

In variation, the composition can further comprise a colorant, whereinthe colorant composition does not comprise water or alcohol. In avariation, colorants are dissolved into the liquid composition or into aNOSDS which is then added to the liquid composition to enhance visualconformation of the evenness of the coating of nitrogen sources'surfaces.

In an embodiment, the NOSDS further comprises the following criteria

-   -   a) is environmentally safe,    -   b) have flashpoints above 145° F.,    -   c) is inherently rated safe for contact with humans and animals,    -   d) forms a liquid solution at between about −20-70° C. of urease        inhibitors comprising a compositional % weight ratio of NOSDS at        between about 40-5% to urease inhibitors at between about 60-95%        for coating the surfaces of nitrogen sources,    -   e) provides an even and effective coating of urease inhibitors        to the surfaces of nitrogen sources particles while not causing        clumping of the particles.

In an embodiment, the composition comprises <5.0% water.

In an embodiment, a method of making dry, flowable urease inhibitorcoated nitrogen sources comprises one or more steps selected from thegroup consisting of

-   -   a) preparing a composition by making a solution of one or more        urease inhibitors in a NOSDS at temperatures between about 20 to        70° C., wherein the urease inhibitors compositional weight        percent range is between about 60 to 95%,    -   b) charging to a separated vessel nitrogen sources particles,    -   c) effectuating agitation of nitrogen sources particles,    -   d) ensuring the temperature range of the nitrogen sources        particles is at between about 20-70° C.,    -   e) charging slowly the composition from “a” nitrogen sources        particles in step “d” while agitating the nitrogen sources        particles,    -   f) continuing agitation of nitrogen sources particles until the        composition has uniformly coated nitrogen sources particle        surfaces,    -   g) cooling the coated nitrogen source particles to packaging        temperature,    -   h) charging flow modifiers to improve the coated nitrogen        sources particles handling and flow properties,    -   i) storing or packaging the urease inhibitor coated nitrogen        sources particles,        wherein the compositional′ weight percent is comprised of        83.33-99.99% nitrogen sources, 10-0.011% urease inhibitors and        6.67-0.0011% NOSDS. In a variation, the urease inhibitor coated        nitrogen sources with high levels of the NOSDS, the urease        inhibitor coated nitrogen sources particles can further comprise        a flow modifier to improve handling and particle flow        properties. In a variation, the flow modifier is a hydrophobic        silica, wherein the hydrophobic silica further comprises        0.25-3.5% of the urease inhibitor coated nitrogen sources.

In an embodiment, a composition further comprising a fertilizer, whereinthe fertilizer is comprised of a) one or more nitrogen sources selectedfrom the group consisting of a) urea, b) urea, formaldehyde reactionproducts, c) urea, formaldehyde, and ammonia reaction products, d)manure, e) dicyandiamide, and f) compost, and wherein the fertilizercomposition weight percent comprises about 83.33-99.99% nitrogensources, 10-0.011% urease inhibitors, and 6.67-0.0011% NOSDS.

In an embodiment, a composition comprises a) one or more ureaseinhibitors and b) a non-aqueous organic solvent delivery system (NOSDS),wherein the NOSDS is comprised of i) dimethyl sulfoxide and optionallyii) one or more solvents selected from the group consisting of aproticsolvents and protic solvents, wherein the one or more urease inhibitorsare selected from the group consisting of i) one or more phosphoramidesand ii) one or more (phosphinic acids organo amines and their salts,wherein the one or more urease inhibitors comprise about 60-95% byweight of said composition, and wherein said composition is liquid at atemperature range between about −20-70° C.

In a variation, the NOSDS comprises dimethyl sulfoxide and one or morenon-aqueous organo solvents selected from the group consisting of a)aprotic solvents and b) protic solvents.

In an embodiment, the composition, wherein the urease inhibitorscomprise one or more phosphoramides selected from the group consistingof a)phosphoric triamides, b) thiophosphoric triamides, and c) alkylthiophosphoric triamides, wherein the alkyl thiophosphoric triamides hasone or more alkyl groups that independently contain between 1 and 6carbon atoms.

In a variation, the one or more urease inhibitors comprise N-(n-butyl)thiophosphoric triamides (NBPT).

In an embodiment, the composition further comprising one or more membersselected from the group consisting of surfactants, buffers,fragrance/odor masking agents, colorants, micro-nutrients, and flowmodifiers, wherein the one or more members do not comprise water andalcohol.

In an embodiment, a method of making a composition for coating nitrogensources comprises one or more steps selected from the group consistingof

-   -   1) heating a composition comprising a NOSDS and one or more        urease inhibitors that are selected from the group consisting        of a) one or more phosphoramides selected from the group        consisting of i) phosphoric triamides, ii) thiophosphoric        triamides, ii) alkyl thiophosphoric triamides, wherein the alkyl        thiophosphoric triamides has one or more alkyl groups that        independently contain between 1 and 6 carbon atoms, b) one or        more phosphinic acid organo amines selected from the group        consisting of i) bis(aminomethyl)phosphinic acids, ii)        aminomethyl(alkylaminomethyl)phosphinic acids, and iii)        di(alkylaminomethy)phosphinic acids, wherein the phosphinic        acids salts are optional, to temperature ranges of between about        20-70° C., and wherein the urease inhibitors are in the % weight        ranges of between about 60-95% of said composition,    -   2) effectuating mixing of the composition,    -   3) holding the mixture to a temperature that the composition is        fluid and optionally the addition of one or more members        selected from the group consisting of surfactants, buffers,        fragrance/odor masking agents, non-water and non-alcohol        containing colorants, micro-nutrients, and flow modifiers.

In an embodiment, the urease inhibitor coated nitrogen sourcescomposition comprises a) one or more nitrogen sources selected from thegroup consisting of i) urea, ii) urea, formaldehyde reaction products,iii) urea, formaldehyde, and ammonia reaction products, iv) manure, v)dicyandiamide, and vi) compost, b) one or more urease inhibitorsselected from the group consisting of i) phosphoramides and ii)phosphinic acids organo amines, and c) a NOSDS, wherein thecomposition's weight percent comprises about 83.33-99.99% nitrogensources, 10-0.011% urease inhibitors, and 6.67-0.0011% NOSDS.

In a variation, the urease inhibitor coated nitrogen sources furthercomprises one or more flow modifiers selected from the group consistingof silicas, hydrophobized silicas, nonionic surfactants, soaps,inorganic powders, and nonionic surfactants, wherein the flow modifierscomprise between about 0.25-3.5 percent weight of said urease inhibitorcoated nitrogen sources.

In an embodiment, a method of making said urease inhibitor coatednitrogen sources comprises one or more steps selected from the groupconsisting of

-   -   a) preparing a composition by making a solution of one or more        urease inhibitors in a NOSDS at temperatures between about 20 to        70° C., wherein the urease inhibitors compositional weight        percent range is between about 60 to 95%, and wherein the        composition is liquid at a temperature range between about        −20-70° C.,    -   b) charging to a separate vessel nitrogen sources particles    -   c) effectuating agitation of nitrogen sources particles,    -   d) ensuring the temperature range of the nitrogen sources        particles is at between about 20-70° C.,    -   e) charging slowly the composition from “a” onto nitrogen        sources particles from step “d” while agitating the nitrogen        sources particles,    -   f) continuing agitation of nitrogen sources particles until the        composition has uniformly coated nitrogen sources particle        surfaces,    -   g) cooling the coated nitrogen source particles to temperatures        ranges of between about 0-60° C.,    -   h) charging flow modifiers to improve the coated nitrogen        sources particles handling and flow properties,    -   i) storing or packaging the urease inhibitor coated nitrogen        sources particles.

In a variation, a method of making urease inhibitor coated nitrogensources comprises one or more nitrogen sources particle formationprocesses selected from the group consisting of

-   -   a) rotating drum granulation,    -   b) fluidized bed granulation, and    -   c) prilling tower,        wherein a composition consist of a) one or more urease        inhibitors and b) a NOSDS and the method of making comprises one        or more steps selected from the group consisting of i) spraying        said composition onto the surfaces of the nitrogen sources        particles during the cooling step of the nitrogen sources        particles formation processes, ii) ensuring the nitrogen sources        particles are at a temperature range of between about 20-70°        C., iii) effectuating the mixing of the particles by air flow or        drum rotation to ensure an even coating of urease inhibitors on        the surfaces of nitrogen source particles.

In a variation, a method of making said urease inhibitor coated nitrogensources comprises one or more nitrogen sources particle formingprocesses selected from the group consisting of

-   -   a) rotating drum granulation,    -   b) fluidized bed granulation,        wherein a composition consist of a) one or more urease        inhibitors and b) a NOSDS and the method of making comprises one        or more steps selected from the group consisting of i) spraying        the composition onto the surfaces of the nitrogen sources        particles while at the end of the spraying of the molten        nitrogen sources step, ii) cooling the temperature of nitrogen        sources particles through air temperature and volume of air flow        that are optimized to ensure limited exposure of composition to        temperature ranges of between about 80-100° C. to minimize        degradation of temperature sensitive urease inhibitors, iii)        effectuating mixing of the particles by air flow or drum        rotation to ensure an even coating of urease inhibitors on the        surfaces of nitrogen source particles.

In another variation, a method of making said urease inhibitor coatednitrogen sources particles that comprises a prilling tower particleformation process, wherein a composition consist of a) one or moreurease inhibitors and b) a NOSDS and the method of making comprises oneor more steps selected from the group consisting of i) spraying saidcomposition onto the surfaces of the nitrogen sources particles towardsupper end the prilling tower where the droplets of the molten nitrogensources are beginning to cool to crystallinity ii) cooling the nitrogensources particles by the counter current air, wherein the air'stemperature and volume of air flow are optimized to ensure limitedexposure of composition to temperature ranges of between about 80-100°C. to minimize degradation of temperature sensitive urease inhibitors,iii) effectuate mixing of the particles using counter current airflowing up the tower to ensure an even coating of urease inhibitors onthe surfaces of nitrogen source particles

In an embodiment, the urease inhibitor coated nitrogen sources canfurther comprise one or more nitrification inhibitors selected from thegroup consisting of 2-chloro-6-trichloromethyl)pyridine,4-amino-1,2,4-6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazineCL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole,ammonium thiosulfate, dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine

In a variation, the NOSDS provides solvating properties to one of morebiologically active agents selected from the group consisting of ureaseinhibitors, nitrification inhibitor(s), pesticide(s), herbicide(s),fungicides(s), and insecticide(s).

In an embodiment, the urease inhibitor coated nitrogen sources canfurther comprise one of more biologically active agents selected fromthe group consisting of nitrification inhibitor(s), pesticide(s),herbicide(s), fungicides(s), and insecticide(s).

In an embodiment, the physical properties of granular and/or prilledurea are positively impacted, wherein the granular and/or prilled iscoated with a concentrated liquid composition comprised of between about60-95% NBPT, between about 4-35% DMSO and between about 1-5% of one ormore members selected from the group consisting of NOSDS other thanDMSO, surfactants, buffers, fragrance/odor masking agents, non-water andnon-alcohol containing colorants, wherein the coated urea composition byweight comprises between about 0.005-0.2%, 0.005-0.1%, 0.005-0.075%,0.005-0.05%, 0.005-0.025%, 0.005-0.01%, 0.005-0.0075%, 0.0075-0.1%,0.01-0.1%, 0.05-0.1%, 0.005-0.15%, and 0.075-0.1% of DMSO.

In an embodiment, urease inhibitors coated nitrogen sources comprisingless than 0.2% DMSO, show an improvement in the relative crush strengthof a nitrogen sources prill and/or granule relative to the same nitrogensources prill and/or granule with no DMSO. In a variation, thiscomposition which comprises between about 0.005-0.2% DMSO shows animprovement in the relative crush strength of a nitrogen sources prilland/or granule relative to the same nitrogen sources prill and/orgranule with no DMSO.

In an embodiment, not to be bound by theory, when urea is contacted byan additive or coating, and wherein the treated urea comprises acompositional weight percent range of between about 0.005-0.2% DMSO, theDMSO penetrates the urea particle causing the crystalline matrix torelax. The DMSO continues to solubilize and move while penetratingdeeper into the urea particle, the structure of the particle re-orientsto a tighter crystalline matrix resulting in improved particle crushstrength.

In an embodiment, urea comprises a compositional weight percent range ofbetween about 0.005-0.2% DMSO has improved crush strength. In avariation, the improved crush strength allows for increases indistribution distances for fertilizer spreaders.

In an embodiment, urease inhibitor coated urea comprises a compositionalweight percent range of between about 0.005-0.2% DMSO has improved crushstrength. In a variation, the improved crush strength allows forincreases in distribution distances for fertilizer spreaders.

In an embodiment, a bio-active agent coated urea comprises acompositional weight percent range of between about 0.005-0.2% DMSO hasimproved crush strength. In a variation, the improved crush strengthallows for increases in distribution distances for fertilizer spreaders

In an embodiment, urea comprises a compositional weight percent range ofbetween about 0.005-0.2% DMSO has improved crush strength. In avariation, the improved crush strength allows for increases indistribution distances for fertilizer spreaders. In another variation,improvements in the distances that the said treated urea can bebroadcasted by hydraulic fertilizer spreaders results in reduced cost offertilization.

In an embodiment, improvements in the distances that the said treatedurea can be broadcasted by hydraulic fertilizer spreaders results inreduced cost of fertilization. In a variation, application ofbio-actives coated urea comprises a compositional weight percent rangeof between about 0.005-0.2% DMSO, which offers end users a cost savingfrom the extended availability of nitrogen through depressing the ureaseenzyme's activities of degrading urea to ammonia and through increasedurea particle hardness. In a variation, the improved urea particlehardness allows for increases in distribution distances for fertilizerspreaders cutting down on the application time for broadcasting thebio-actives coated urea and less cleaning of equipment during theapplication of bio-actives coated urea to plant growth mediums.

Example 1

6.84 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine and 0.11grams of FD&C Blue #1 were charged to a vessel, placed under agitationand then heated to 60° C. 33.0 grams of N-(n-butyl)thiophosphorictriamide was then slowly charged to the vessel, and mixed at 45-55 Cuntil completely dissolved. Once dissolved, the mixture was prepared forapplication to the surface of a powder or granular nitrificationinhibitor.

Example 2

5.44 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine, 1.4grams of propylene glycol and 0.11 grams of FD&C Blue #1 were charged toa vessel, placed under agitation and then heated to 60° C. 33.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 3

7.0 grams of propylene glycol were charged to a vessel, placed underagitation and then heated to 60° C. 33.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 4

5.44 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine, 1.4grams of ethylene glycol and 0.11 grams of FD&C Blue #1 were charged toa vessel, placed under agitation and then heated to 60° C. 33.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 5

4.48 grams of dimethyl sulfoxide, 0.05 grams of triethanolamine, 1.4grams of glycerin and 0.11 grams of FD&C Blue #1 were charged to avessel, placed under agitation and then heated to 60° C. 34.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 6

5.44 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine, 1.4grams of tripropylene glycol methyl ether (TPM) and 0.11 grams of FD&CBlue #1 were charged to a vessel, placed under agitation and then heatedto 60° C. 33.0 grams of N-(n-butyl)thiophosphoric triamide was thenslowly charged to the vessel, and mixed at 45-55 C until completelydissolved. Once dissolved, the mixture was prepared for application tothe surface of a powder or granular nitrification inhibitor.

Example 7

5.44 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine, 1.4grams of ethyl lactate and 0.11 grams of FD&C Blue #1 were charged to avessel, placed under agitation and then heated to 60° C. 33.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 8

5.44 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine, 1.4grams of triethylphosphate and 0.11 grams of FD&C Blue #1 were chargedto a vessel, placed under agitation and then heated to 60° C. 33.0 gramsof N-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 9

5.44 grams of dimethyl sulfoxide, 0.06 grams of triethanolamine, 1.4grams of polyethylene glycol 400 and 0.11 grams of FD&C Blue #1 werecharged to a vessel, placed under agitation and then heated to 60° C.33.0 grams of N-(n-butyl)thiophosphoric triamide was then slowly chargedto the vessel, and mixed at 45-55 C until completely dissolved. Oncedissolved, the mixture was prepared for application to the surface of apowder or granular nitrification inhibitor.

Example 10

4.48 grams of dimethyl sulfoxide, 0.05 grams of triethanolamine, 1.4grams of dipropylene glycol methyl ether acetate and 0.11 grams of FD&CBlue #1 were charged to a vessel, placed under agitation and then heatedto 60° C. 34.0 grams of N-(n-butyl)thiophosphoric triamide was thenslowly charged to the vessel, and mixed at 45-55 C until completelydissolved. Once dissolved, the mixture was prepared for application tothe surface of a powder or granular nitrification inhibitor.

Example 11

4.48 grams of dimethyl sulfoxide, 1.5 grams of triethanolamine and 0.11grams of FD&C Blue #1 were charged to a vessel, placed under agitationand then heated to 60° C. 34.0 grams of N-(n-butyl)thiophosphorictriamide was then slowly charged to the vessel, and mixed at 45-55 Cuntil completely dissolved. Once dissolved, the mixture was prepared forapplication to the surface of a powder or granular nitrificationinhibitor.

Example 12

4.48 grams of dimethyl sulfoxide, 0.05 grams of triethanolamine, 1.4grams of propylene carbonate and 0.11 grams of FD&C Blue #1 were chargedto a vessel, placed under agitation and then heated to 60° C. 34.0 gramsof N-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 13

4.48 grams of dimethyl sulfoxide, 0.05 grams of triethanolamine, 1.4grams of dimethyl glutarate and 0.11 grams of FD&C Blue #1 were chargedto a vessel, placed under agitation and then heated to 60° C. 34.0 gramsof N-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 14

4.48 grams of dimethyl sulfoxide, 0.05 grams of triethanolamine, 1.4grams of sorbitol and 0.11 grams of FD&C Blue #1 were charged to avessel, placed under agitation and then heated to 60° C. 34.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 15

4.48 grams of dimethyl sulfoxide, 0.05 grams of triethanolamine, 1.4grams of isopropylidene glycerol and 0.11 grams of FD&C Blue #1 werecharged to a vessel, placed under agitation and then heated to 60° C.34.0 grams of N-(n-butyl)thiophosphoric triamide was then slowly chargedto the vessel, and mixed at 45-55 C until completely dissolved. Oncedissolved, the mixture was prepared for application to the surface of apowder or granular nitrification inhibitor.

Example 16

7.0 grams of propylene carbonate were charged to a vessel, placed underagitation and then heated to 60° C. 33.0 grams ofN-(n-butyl)thiophosphoric triamide was then slowly charged to thevessel, and mixed at 45-55 C until completely dissolved. Once dissolved,the mixture was prepared for application to the surface of a powder orgranular nitrification inhibitor.

Example 17

5.44 grams of tetramethylene sulfoxide, 0.06 grams of triethanolamine,1.4 grams of propylene glycol and 0.11 grams of FD&C Blue #1 werecharged to a vessel, placed under agitation and then heated to 60° C.33.0 grams of N-(n-butyl)thiophosphoric triamide was then slowly chargedto the vessel, and mixed at 45-55 C until completely dissolved. Oncedissolved, the mixture was prepared for application to the surface of apowder or granular nitrification inhibitor.

Example 18

6.84 grams of dimethyl formamide, 0.06 grams of triethanolamine and 0.11grams of FD&C Blue #1 were charged to a vessel, placed under agitationand then heated to 60° C. 33.0 grams of N-(n-butyl)thiophosphorictriamide was then slowly charged to the vessel, and mixed at 45-55 Cuntil completely dissolved. Once dissolved, the mixture was prepared forapplication to the surface of a powder or granular nitrificationinhibitor.

Example 19

5.44 grams of tetramethylene sulfone (sulfolane), 0.06 grams oftriethanolamine, 1.4 grams of propylene glycol and 0.11 grams of FD&CBlue #1 were charged to a vessel, placed under agitation and then heatedto 60° C. 33.0 grams of N-(n-butyl)thiophosphoric triamide was thenslowly charged to the vessel, and mixed at 45-55 C until completelydissolved. Once dissolved, the mixture was prepared for application tothe surface of a powder or granular nitrification inhibitor.

Example 51

6.9 grams of dimethyl sulfoxide, and 0.11 grams of FD&C Blue #1 werecharged to a vessel, placed under agitation and then heated to 60° C.33.0 grams of N-(n-butyl)thiophosphoric triamide was then slowly chargedto the vessel, and mixed at 45-55 C until completely dissolved. Oncedissolved, the mixture was prepared for application to the surface of apowder or granular nitrification inhibitor.

(Note: Table 1 has been split into Table 1a and 1b to accommodate theamount of data)

TABLE 1a Chart of NBPT Examples 1-10 Examples 1 2 3 4 5 6 7 8 9 10 NBPT33.0 33.0 33.0 33.0 34.0 33.0 33.0 33.0 33.0 34.0 DMSO 6.84 5.44 5.444.48 5.44 5.44 5.44 5.44 4.48 Blue dye 0.11 0.11 0.11 0.11 0.11 0.110.11 0.11 0.11 Propylene Glycol 1.4 7 Ethylene Glycol 1.4 Glycerin 1.4TPM 1.4 Ethyl Lactate 1.4 PEG 400 1.4 DPMAc 1.4 Triethanolamine 0.060.06 0.06 0.05 0.06 0.06 0.06 0.06 0.05 Propylene Carbonate DimethylGlutarate Sorbitol triethyl phosphate 1.4 Isopropylidene GlycerolTetramethylene sulfoxide Dimethyl formamide Tetramethylene sulfone Total40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 % NBPT 80.0 80.0 80.080.0 82.4 80.0 80.0 80.0 80.0 82.4 Dispersion Stability 1 1 4 1 2 1 1 11 2 @ 50 C. Stability rating: 1 = stable, 5 = split @ 6 hrs/50 C. NBPT =N-(n-butyl)thiophosphoric triamide; DMSO = dimethyl sulfoxide; Blue Dye= FD&C Blue #1; TPM = Tripropylene glycol monomethyl ether; PEG 400 =polyethylene glycol/molecular weight of 400 units; DPMAc = Dipropyleneglycol monomethyl ether acetate capped

TABLE 1b Chart of NBPT Examples 11-20 Examples 11 12 13 14 15 16 17 1819 51 NBPT 34.0 34.0 34.0 34.0 34.0 33.0 33.0 33.0 33.0 33.0 DMSO 4.484.48 4.48 4.48 4.48 6.89 Blue dye 0.11 0.11 0.11 0.11 0.11 .11 .11 .11.11 0.11 Propylene Glycol 1.4 1.4 Ethylene Glycol Glycerin TPM EthylLactate PEG 400 DPMAc Triethanolamine 1.5 0.05 0.05 0.05 0.05 Propylene1.4 7 Carbonate Dimethyl 1.4 Glutarate Sorbitol 1.4 triethyl phosphateIsopropylidene 1.4 Glycerol Tetramethylene 5.44 sulfoxide Dimethyl 6.84formamide Tetramethylene 5.44 sulfone Total 40.0 40.0 40.0 40.0 40.040.0 40.0 40.0 40.0 40 % NBPT 82.4 82.4 82.4 82.4 82.4 80.0 80 80 80 80Dispersion 3 1 1 1 1 5 1 1 1 1 Stability @ 50 C. Stability rating: 1 =stable, 5 = split @ 6 hrs/50 C. NBPT = N-(n-butyl)thiophosphorictriamide; DMSO = dimethyl sulfoxide; Blue Dye = FD&C Blue #1; TPM =Tripropylene glycol monomethyl ether; PEG 400 = polyethyleneglycol/molecular weight of 400 units; DPMAc = Dipropylene glycolmonomethyl ether acetate capped

The examples of the urease inhibitor/NOSDS formulations innovationsdemonstrate the flexibility technology in producing stable, liquidsamples with concentrations of 80-83% of urease inhibitors. Theprocedure for producing Examples 20-45 is as follows:

-   -   1. 186.1 grams of solid powder or granular nitrification        inhibitor were heated to 60° C. in a glass vessel and mixed        using an overhead stirrer with anchor agitator.    -   2. 13.90 grams of one of the formulations from the Examples 1-20        @ 45-55 C was slowly dripped onto the agitating solid powder or        granular nitrification inhibitor.    -   3. The combination was mixed at 60 RPMs for 120 seconds and then        poured into an 16 oz. jar and tapped on the table top 5 times    -   4. The coated solid powder or granular nitrification inhibitor        was evaluated for flow, quality of urease inhibitor coating,        time for dissolution in distilled water and in a 30% UAN        solution (urea/ammonium nitrate solution in water).

The “coating quality rating” was based on a visual assessment ofcoverage of nitrification particles by utilizing the incorporated bluedye. Ratings were from 1-5 where 1=poor coverage showing large patchesof non-blue particles versus 5=excellent coverage as determined by thecontinuity of the blue color and no non-blue patches. The “packingflowability rating” was based on a visual assessment of:

-   -   1. Pouring 200 grams of coated nitrification particles into a        quart jar and capping with lid.    -   2. Sharply tapping the quart jar on a hard surface five times    -   3. After 24 hours of setting at room temperature, flip jar over.        If material remains in the jar's original bottom, a small        spatula's wooded handle is used to gently tap the jar's bottom.    -   4. Ratings were from 1-5 where 1=poor flowability where material        did not fall after 5 taps versus 5=excellent flowability where        all the material falls without a tap.

Urease Formulation Coating Performance

TABLE 2 Coating Performance on Nitrification Inhibitors FlowabilityRating: 1 = lumps and Coating Nitrifi- Coating rating: poor flow;Example cation 1 = poor; 5 = good flow Example# # inhibitor 5 = fullcoating (1 tap max) 20 1 DCD 5 3 21 2 DCD 5 5 22 4 DCD 5 4 23 5 DCD 5 324 6 DCD 5 3 25 7 DCD 4 4 26 9 DCD 5 2 27 10 DCD 5 3 28 11 DCD 4 3 29 12DCD 4 3 30 14 DCD 4 3 31 15 DCD 5 3 32 16 DCD 5 3 33 17 DCD 5 5 34 18DCD 4 4 35 19 DCD 5 5 36 1 STS 5 2 37 2 STS 5 1 38 6 STS 5 4 39 7 STS 51 40 8 STS 5 1 41 1 Np 5 1 42 2 Np 5 2 43 6 Np 5 3 44 7 Np 5 1 45 8 Np 51 46 51 DCD 5 3 {circumflex over ( )} DCD = Dicyandiamide; STS = SodiumThiosulfate; Np = Nitrapyrin

The performance of the examples of urease inhibitors/NOSDS formulationinnovations in coating nitrification inhibitor powders and granules andthe flowability of the coated nitrification inhibitors without utilizingflow aid additives demonstrates the ease of use and the commercialviability of the innovation.

Nitrification Inhibitor Coated with Urease Formulation Time toDissolution

-   -   1. In a 4 oz. glass jar add 97 grams of either Deionized (DI)        Water or UAN 30.    -   2. Add a ¾ inch magnetic stir bar and place on a Corning/Model        PC-420 Heater/Stirrer and set stirring speed at #7.    -   3. Charge 3 grams of a nitrification inhibitor coated or        uncoated and start stop watch.    -   4. Visually determine the point at which all particles of the        nitrification inhibitor have dissolved and record this time as        time to dissolution.

TABLE 3 DCD Coated with an NBPT Concentrate in NOSDS: Time toDissolution DI Water UAN 30 Time to Time to % Coated Dissolution InitialDissolution Initial Sample ID Nitrification (seconds) Appearance(seconds) Appearance DCD 3% X X 1740 clear untreated Example 21 3% 1170 clear 1342 clear *Commercial 3% Infinitely Cloudy with Infinite Cloudywith Product insoluble small particles insoluble small particles Example20 3% 995 Clear 1170 Clear Example 21 3% 915 Clear 1125 Clear Example 223% 885 Clear 1220 Clear Example 23 3% 970 Clear 1450 Clear Example 24 3%905 Clear 1295 Clear Example 25 3% 975 Clear 1265 Clear Example 26 3%1000  Clear 1365 Clear Example 27 3% 1030  Clear 1265 Clear Example 283% 885 Clear 1310 Clear Example 29 3% 870 Clear 1334 Clear Example 30 3%890 Clear 1185 Clear Example 31 3% 910 Clear 1140 Clear Example 46 3 985 Clear 1740 Clear *Commercial Product = Agrotain Plus EZ Flow

The performance of the coated DCD examples demonstrates the improvedsolubility of these innovations over uncoated DCD and over a commercialNBPT/DCD product. The clarity of the coated DCD innovations in a UANsolution will result in improvements in the evenness of application ofboth urease and nitrification inhibitors. Technologies based on aninsoluble urea formaldehyde particle coated with NBPT blended with a dryDCD will result in cloudy UAN solutions that require continuousagitation to maintain homogeneity of the suspended particles. Applyingsuch a UAN solution on a field utilizing standard spraying equipmentresults in uneven in application of inhibitors

TABLE 4 Ammonium Thiosulfate Coated with an NBPT Concentrate in NOSDS:Time to Dissolution DI Water UAN 30 Time to Time to % Coated DissolutionInitial Dissolution Initial Sample ID Nitrification (seconds) Appearance(seconds) Appearance Example 36 3% X X 240 Clear Example 37 3% X X 230Clear Example 38 3% X X 275 Clear Example 39 3% X X 260 Clear Example 403% X X 300 Clear

To determine what minimum effective levels of DCD are required to meetacceptable levels of nitrification inhibition and to maximizeperformance versus inhibitor level, studies were performed at AuburnUniversity, South Dakota State University and University of Arkansas.These studies were performed by coating urea with a liquid nitrificationinhibitor product, trade name N Bound, which contained approximately 28%DCD. The application rates of N Bound on urea (Units are in quarts of NBound/ton of urea) was varied to measure application level versus theconversion of urea to nitrate measured as mg NO₃ extracted from theapplied soil.

Example 47

A trial conducted at University of Arkansas was designed to measure andcompare the nitrate concentrations from the microbial activity onuntreated urea and ureas coated with N Bound that had been applied toclassified as a Calhoun silt loam (pH=7.4) at varying rates. Theobjective was to determine the minimum inhibitor application rate toachieve optimize nitrification inhibition. The statistical results arelisted in Table 5.

TABLE 5 Nitrate-N Concentration (mg NO₃—N/kg soil) Table 5. Productapplication rates and nitrification of urea fertilizer during a 35 dayincubation Day 1 Day 3 Day 7 Day 14 Day 21 Day 28 Day 35 Untreated Soil(check) 112.2 99.4 115.4 143.7 141.4 175.8 151.2 Urea 113.4 98.6 151.6202.8 221.2 262.3 255.3 Urea + Liquid DCD 111.6 97.2 141.5 199.3 223.1271.4 259.4 product (4 qt/T) Urea + Liquid DCD 112.8 96.2 143.7 197.9216.9 251.0 268.9 product (6 qt/T) Urea + Liquid DCD 113.1 99.4 139.9176.8 203.1 245.8 258.3 product (8 qt/T)The results of the trial show nitrification control through 21 days at arate of 8 qt N-Bound/ton is used.

Example 48

A trial conducted at the South Dakota State was designed to measure andcompare the nitrate concentrations from the microbial activity onuntreated urea and ureas coated with N Bound that had been applied toMidwestern soil at varying rates. The graph in FIG. 1 shows the resultsof the experiment. The results of the experiment conclude that N Boundapplied at 7 lbs/ton or more resulted in more plant available nitrogen(ammonium and nitrate nitrogen after 35 days of storage versus lower NBound application levels.

Example 49

A trial conducted at the Auburn University was designed to measure andcompare the nitrate and ammonical nitrogen concentrations from themicrobial activity on untreated urea and ureas coated with N Bound thathad been applied a wetted Marvyn loamy sand, (approximately 80% sand) atvarying rates. The graph in FIG. 2 shows the results of the experiment.The results of the experiment conclude that in the 8 week incubationstudy, N Bound applied to urea at 8 qts/Ton of urea exhibitedsignificant nitrification inhibitory properties versus lower N Boundapplication levels.

Table 6 shows the conversion of the data in Example 46, 47, and 48 of NBound application levels to percentages of N Bound on urea. Table 2 alsoconverts N Bound application levels to DCD application levels on ureaand on the basis of the nitrogen present in urea.

TABLE 6 **** % DCD based on *Quarts of N nitrogen Testing Bound/ton of**% N Bound ***% DCD content Entity urea on urea on urea of urea SouthDakota 7 0.84% 0.24% 0.51% State University Auburn 8 0.97% 0.27% 0.59%University University 8 0.97% 0.27% 0.59% of Arkansas *N Bound (tradename of EcoAgro Resources) is DCD dispersed in a non-aqueous solventsystem. **Specific gravity of N Bound (lbs/gal) = 9.6512 ***% DCD = 28%**** % N in urea = 46%

For dry urea, liquid systems containing DCD have the advantage of evendistribution of inhibitors over the surface of urea. Liquid productscontaining and urease and nitrification inhibitors offer the samebenefit. However, the drawback is that coating levels exceeding 0.75% ofcurrent liquid systems have processability issues in mixing andapplication equipment with the formation of clogs and high level ofdeposition of the fertilizer requiring more frequent cleaning and theformation of clumps of fertilizer impacting evenness of application.Coating levels of <0.75% of such a liquid product can be achieved withapplication of a maximum of 6 qts liquid product/ton of urea. However,this results in an application level of DCD at 0.20% which is below theminimum effective level as established in the above studies.

Example 50

A trial conducted at the West Texas State University was designed tomeasure and compare the headspace analysis of ammonia concentrationsformed from urease activity on untreated urea and ureas coated with NYield that had been applied western US soils at varying rates. The graphin FIG. 3 shows the results of the experiment. The results of theexperiment conclude N Yield applied to urea at 2 qts/Ton of ureaexhibited significant urease inhibitory properties versus lower N Yieldapplication levels. Table 7 shows the conversion of the data in FIG. 3of N Yield application levels to percentages of N Yield on urea. Table 7also converts N Yield application levels to NBPT application levels onurea and on the basis of the nitrogen present in urea.

TABLE 7 **** % NBPT required **% for *Quarts N liquid **% nitrogenTesting Yield/ton NBPT NBPT content Entity of urea on urea on urea ofurea West 0.5 0.06% 0.02% 0.03% Texas 1 0.11% 0.03% 0.07% State 2 0.23%0.06% 0.13% University 4 0.45% 0.12% 0.26% *N Yield (trade name ofEcoAgro Resources) is NBPT dispersed in a non-aqueous solvent system.**Specific gravity of N Yield (lbs/gal) = 9.08 ***% NBPT = 26.7% **** %N in urea = 46%

For dry urea, liquid systems containing NBPT have the advantage of evendistribution of inhibitors over the surface of urea. Liquid productscontaining and urease and nitrification inhibitors offer the samebenefit. However, while liquid coating containing NBPT are well underthe 0.75% level, coating urea with both DCD and urease inhibitorsrequire application levels that exceed 0.75%. This results in coatedurea having processability issues in mixing and application equipmentwith the formation of clogs and high level of deposition of thefertilizer requiring more frequent cleaning and the formation of clumpsof fertilizer impacting evenness of application.

Example 51

A sample of (hexylaminomethylene, aminomethylene) phosphinic acid,(C₈H₂₀N₂O₂P), was prepared by charging 132 grams of hypophosphorousacid/50% water to a reaction vessel and then charging 60 grams ofparaformaldehyde while agitating. Cooling was applied to assist inmaintaining the temperature below 50° C. The composition was then heatedto 70° C. and held at 70° C. until the composition cleared. Thetemperature was cooled to 25-30° C. and then 101.19 grams of hexylaminewas slowly charged in order to maintain the temperature <40 C. Aftercompleting the hexylamine charge, temperature was raised to 70° C. overa two hour period and then held for one hour or until composition'sappearance became clear. Once appearance became clear, a sub-surfacecharging of ammonia gas began. The NH₃ sparge continued at a temperatureof 70° C. until the composition's 10% pH reached 7.5-8.5 and then thecomposition was then heated to 90° C. over a one hour period. Duringthis time, the composition's 10% pH was held at 7.5-8.5 by adjusting thepH through ammonia sparging. The composition was held at 90° C. for onehour while maintain 10% pH at 7.5-8.5 by adjusting the pH throughammonia sparging. After 1 hour at 90° C., vessel pressure was reducedthrough application of a vacuum until the pressure reading was 80-100 mmHg to strip out excess ammonia and some water until distillationstopped.

Example 52

A sample of (hexylaminomethylene, aminomethylene) phosphinic acid,(C₈H₂₀N₂O₂P), was prepared by charging 132 grams of hypophosphorousacid/50% water and 20 grams propylene carbonate to a reaction vessel.Reaction vessel was heated to 70° C. and water stripped out until %moisture ≤5% under reduced pressure. After composition was cooled to30-40° C., the reaction proceeded with charging 46 grams of dimethylsulfoxide and then slowly charging 60 grams of trioxane while agitating.The composition was then heated to 70° C. and held at 70° C. until thecomposition cleared. The temperature was cooled to 25-30° C. and then101.19 grams of hexylamine was slowly charged in order to maintain thetemperature <40° C. After completing the hexylamine charge, thetemperature was raised to 70° C. over a two hour period and then heldfor one hour or until the composition's appearance became clear. Oncethe appearance became clear, a sub-surface charging of ammonia gasbegan. The NH₃ sparge continued at a temperature of 70° C. until thecomposition's 10% pH reached 7.5-8.5 and then the composition was thenheated to 90° C. over a one hour period. During this time, thecomposition's 10% pH was held at 7.5-8.5 by adjusting the pH throughammonia sparging. The composition was held at 90° C. for one hour whilemaintain 10% pH at 7.5-8.5 by adjusting the pH through ammonia sparging.After 1 hour at 90° C., the vessel pressure was reduced throughapplication of a vacuum until the pressure reading was ≤20 mm Hg tostrip out excess ammonia and water. The vacuum was maintained untildistillation ceased and % moisture was less than 5%. The 10% pH wasrechecked and extra NH₃ gas was sparged to adjust the pH to 7.5-8.0. Thecomposition was cooled and packaged.

Example 53

120 grams of Example 51 and 36 grams of ethylene glycol were charged toa reaction vessel and heated to 90° C. The vessel pressure was reducedthrough application of a vacuum until the pressure reading was ≤20 mm Hgto strip out excess ammonia and water. The vacuum was maintained untildistillation ceased and % moisture was less than 5%. The composition wascooled and packaged.

Example 54

Ammonia Volatilization Screening Test for Urease Inhibitors Beforetesting example Nos 51 and 52 performances as a coating on nitrificationinhibitor granules, the examples were validated for performance asurease inhibitors by comparing the ammonia volatilization of treatedurea versus untreated urea. The treated urea was prepared as follows:

Sample Preparation for Application to Urea Example 55

Example 52 actives were adjusted to 30% by dilution with DMSO.

Example 56

Example 53 actives were adjusted to 30% by dilution with DMSO

Example 57

Example 51 actives were adjusted to 30% by dilution with 50/50DMSO/Water

Example 58

30.92 grams N-(n-butyl) thiophosphoric triamide was dissolved in 69.08grams of a 50/50 DMSO/propylene glycol

Examples Application to Urea

Urea was coated with an example by:

-   -   1. Charging weight of urea as directed by Table 8 to a        container.    -   2. The urea was slowly agitated with overhead stirrer with U        shaped agitator blade.    -   3. The example was slowly dripped on the urea while mixing in        the amount as directed by Table 8 (rate=3 quarts/ton of urea).    -   4. When the proper weight of the example had been charged the        mixing speed was increased to ensure adequate coating of the        urea by the example.    -   5. The coated urea was placed in a jar and sealed.

TABLE 8 Formulation for treating urea Example Example Example ExampleCompound 59 60 61 62 Urea 199.28 grams 199.28 199.28 199.28 Example 550.72 grams Example 56 0.72 grams Example 57 0.72 grams Example 58 0.72grams

Preparing Test Soil

-   -   1. In a 6″×9″ rectangular Tupperware sealable container with        holes drilled on each end and sealed with tape charge 400 grams        of West Texas Sandy Loam Soil and 100 grams of distilled water,        mix thoroughly to a consistency of thick “mud” (% moisture        should be between 30-40%).    -   2. Calculate the surface area to be treated.        -   a. 6″×9.5″=sq in/144 sq in/sq ft=0.395 sq ft        -   b. 0.395 sq ft/43,560 sq ft/acre=0.0000091 acres    -   3. Calculate amount of urea and treated urea to charge to the        containers of soil        -   a. Application Rate: 400 pounds urea per acre        -   b. 400 lbs/acre/43560 sq ft/acre=0.009 lbs/sq ft×0.395 sq            ft/container=0.0036 lbs/container×454 g/lb=1.65 grams urea            per container.        -   c. Add 1.65 grams of urea and various treated ureas to each            container    -   4. Ammonia Volatilization Screening Test        -   a. Evenly distribute over the soil in each container 1.65            grams of example to be tested,        -   b. Seal container,        -   c. Take readings of ammonia volatilization of each container            over a selected period of time as directed in Table 9,            -   i. Drager tube measurement                -   (1) Use Drager pump with 0-600 ppm (or range TBD)                    ammonia drager tube.                -   (2) At specified times, quickly remove the tape on                    one end of container and insert the drager                    tube/pump.                -   (3) Fully squeeze pump 20 times allowing enough time                    for pump to fully inflate between each squeeze and                    then remove the tube from the container and read.                -   (4) Open container lid and vent the remaining                    ammonia gas out of the container and reseal.                -   (5) Repeat procedure at next designated time.

TABLE 9 Ammonia Volatilization Test Results Ammonia Reading (ppm)Example ID 72 hours 144 hours 264 hours Urea 220 475 460 # 59 50 120 200# 61 50 110 220 # 62 90 210 600The performance of the examples of the new urease inhibitors/NOSDSformulations in slowing the generation of ammonia from the degradationof urea by urease enzyme show these examples perform better than thestandard urease inhibitor N-(n-butyl) thiophosphoric triamide.

The procedure for producing DCD coated examples from examples 51-53 isas follows:

-   -   1. 186.1 grams of solid powder or granular nitrification        inhibitor were heated to 60° C. in a glass vessel and mixed        using an overhead stirrer with anchor agitator.    -   2. 13.90 grams of one of the formulations from the Examples        51-53 @ 45-55° C. was slowly dripped onto the agitating solid        powder or granular nitrification inhibitor.    -   3. The combination was mixed at 60 RPMs for 120 seconds and then        poured into an 16 oz. jar and tapped on the table top 5 times.    -   4. The coated solid powder or granular nitrification inhibitor        was evaluated for flow, quality of urease inhibitor coating.        -   The “coating quality rating” was based on a visual            assessment of coverage of nitrification particles by            utilizing the incorporated blue dye. Ratings were from 1-5            where 1=poor coverage showing large patches of non-blue            particles versus 5=excellent coverage as determined by the            continuity of the blue color and no non-blue patches. The            “packing flowability rating” was based on a visual            assessment of:    -   1. Pouring 200 grams of coated nitrification particles into a        quart jar and capping with lid.    -   2. Sharply tapping the quart jar on a hard surface five times.    -   3. After 24 hours at room temperature, flip jar over. If        material remains in the jar's original bottom, a small spatula's        wooded handle is used to gently tap the jar's bottom.    -   4. Ratings were from 1-5 where 1=poor flowability where material        did not fall after 5 taps versus 5=excellent flowability where        all the material falls without a tap.

Urease Formulation Coating Performance

TABLE 10 Coating Performance on Nitrification Inhibitors Coating rating:Flowability Rating: Nitrification 1 = poor; 1 = lumps and poor flow;Example# inhibitor 5 = full coating 5 = good flow (1 tap max) 51 DCD 3 352 DCD 5 4 53 DCD 5 5 {circumflex over ( )} DCD = Dicyandiamide

Example #53 showed the best performance of the 3 examples of ureaseinhibitors/NOSDS formulation in coating nitrification inhibitorparticles. The resulting flowability of the coated nitrificationinhibitors without utilizing flow aid additives demonstrates the ease ofuse. Example 51 shows the negative impact of water on coating and onflowability.

Example 63

240 grams of hypophosphorous acid/50% in water and 60 grams of propylenecarbonate were charged to a reaction vessel. The contents were placedunder a vacuum of 25-35 mm and heated to 90° C. Approximately 107 gramsof water were removed. 93.1 grams of the stripped hypophosphorous acidand propylene carbonate were charged to another reaction vessel andcooled to 30° C. 56.47 grams of 1,3,5-trioxane and 111.74 of DimethylSulfoxide were charged to the reaction vessel and mixed until thetrioxane was dissolved. The contents were heated to 75° C. over a 6 hourperiod and then held a 75° C. for 30 minutes. The contents were cooledto 40-50° C. and then 95.16 grams of n-hexylamine was slowly chargedover an hour to the reactor while holding the temperature at 40-45° C.The contents were then heated to 80° C. over a three hour period. Avacuum of 20-30 mm was established and the reaction vessel contents werestripped of water content changing appearance of contents from murky toclear. Contents were cooled to 60° C. and then ammonia gas was chargedsubsurface to the contents while maintaining temperature at 60-80° C.When approximately ½ of the ammonia gas (8 grams) had been charged, theammonia charge was halted and a vacuum of 20-30 mm was established andthe reaction vessel contents were stripped of water content changingappearance of contents from murky to clear. The subsurface charging ofthe ammonia gas was re-started and continued until the pH was at 8.2.The contents were heated to 110° C. and held for 30 minutes. Thesubsurface charging of ammonia gas was started as the contents werecooled to 80° C., the pH was measured at 8.6 and the ammonia gas chargewas halted. A vacuum of 20-30 mm was established and the reaction vesselcontents were stripped of water content changing appearance of contentsfrom murky to clear. The contents were cooled and packaged.

Example 64

91.13 grams of hypophosphorous acid/50% in water and 44.19 grams ofDimethyl Sulfoxide were charged to a reaction vessel. 41.84 grams ofparaformaldehyde and 22.78 grams of Dimethyl Sulfoxide for rinsing werecharged to the reaction vessel and mixed until the paraformaldehyde wasdispersed and its exotherm completed. The contents were heated to 70° C.over a 2 hour period and then heated a 100° C., held for 30 minutes andthen the contents were cooled to 27° C. and then 89.21 grams ofaminoethylpiperzine was slowly charged over an hour to the reactor whileholding the temperature at 40-45° C. The contents were then heated to100° C. over a one hour period. Contents were cooled to 44.3° C. andthen ammonia gas was charged subsurface to the contents whilemaintaining temperature at 60-80° C. The subsurface charging of theammonia gas was started and continued until the pH was at 8.2. Thecontents were heated to 110° C. and held for 60 minutes. The contentswere cooled to 88° C., the pH was measured at 7.9 and a vacuum of 20-30mm was established and the reaction vessel contents were stripped ofwater content. Approximately 46.6 grams of distillate were recovered anda yield of 71.27%. The contents were cooled and packaged.

Example 65

97.18 grams of hypophosphorous acid/50% in water and 47.12 grams ofDimethyl Sulfoxide were charged to a reaction vessel. 44.61 grams ofparaformaldehyde and 24.29 grams of Dimethyl Sulfoxide for rinsing werecharged to the reaction vessel and mixed until the paraformaldehyde wasdispersed and its exotherm completed. The contents were heated to 70° C.over a 2 hour period and then heated a 100° C., held for 30 minutes andthen the contents were cooled to 44.3° C. and then 75.22 grams ofdimethylaminopropylamine was slowly charged over an hour to the reactorwhile holding the temperature at 40-45° C. The contents were then heatedto 100° C. over a one hour period. Contents were cooled to 22.4° C. andthen ammonia gas was charged subsurface to the contents whilemaintaining temperature at 60-80° C. The subsurface charging of theammonia gas was started and continued until the pH was at 8.6. Thecontents were heated to 110° C. and held for 60 minutes. The contentswere cooled to 88° C., the pH was measured at 8.1 and a vacuum of 20-30mm was established and the reaction vessel contents were stripped ofwater content. Approximately 78.7 grams of distillate were recovered anda yield of 58.47%. The contents were cooled and packaged.

Example 66

91.12 grams of hypophosphorous acid/50% in water and 44.18 grams ofDimethyl Sulfoxide were charged to a reaction vessel. 41.83 grams ofparaformaldehyde and 22.78 of Dimethyl Sulfoxide for rinsing werecharged to the reaction vessel and mixed until the paraformaldehyde wasdispersed and its exotherm completed. The contents were heated to 70° C.over a 2 hour period and then heated a 100° C., held for 30 minutes andthen the contents were cooled to 37.8° C. and then 100.97 grams ofn-butylamine was slowly charged over an hour to the reactor whileholding the temperature at 40-45° C. and hold fro 1.5 hours. Thecontents were then heated to 110° C. over a four hour period. Contentswere cooled to 60° C. and then ammonia gas was charged subsurface to thecontents while maintaining temperature at 60-80° C. The subsurfacecharging of the ammonia gas was started and continued until the pH wasat 8.1. A vacuum of 20-30 mm was established and the reaction vesselcontents were stripped of water content. Approximately 59.87 grams ofdistillate were recovered and a yield of 60.07%. The contents werecooled and packaged.

Example 67

50 grams of a 50% ammonia neutralized polyaspartic acid in DMSO was mixwith 50 grams of Example 63 for 30 minutes. Sample was clear andpackaged.

Example 68

50 grams of a 34% solution of DCD in DMSO was mix with 50 grams ofExample 63 for 30 minutes. Sample was clear and packaged.

Example 69

50 grams of a 50% N-(n-butyl) thiophosphoric triamide in DMSO was mixwith 50 grams of Example 63 for 30 minutes. Sample was clear andpackaged.

Example 70

50 grams of a 50% N-(n-butyl) thiophosphoric triamide in DMSO was mixwith 50 grams of Example 65 for 30 minutes. Sample was clear andpackaged.

Example 71

50 grams of a 34% solution of DCD in DMSO was mix with 50 grams ofExample 64 for 30 minutes. Sample was clear and packaged.

Example 72

50 grams of a 34% solution of DCD in DMSO was mix with 50 grams ofExample 66 for 30 minutes. Sample was clear and packaged.

Example 73

50 grams of a 44% solution of DCD-formaldehyde reaction product in DMSOwas mix with 50 grams of Example 63 for 30 minutes. Sample was clear andpackaged.

Example 74

35 grams of a 44% solution of DCD-formaldehyde reaction product in DMSOwas mix with 35 grams of a 30% solution of polysuccinimide and 30 gramsof Example 63 for 30 minutes. Sample was clear and packaged.

Example 75

1.44 grams of tripropylene glycol mono methyl ether (TPM) and 4.83 gramsof dimethyl sulfoxide (DMSO) were heated to 55° C. under agitation. Next92.85 grams of N(n-butyl) thiophosphoric triamide (NBPT) powder was veryslowly charged initially allowing small portions to be solubilizedbefore adding more powder. Once the NBPT has been completelysolubilized, 0.24 grams of a scent package and 0.05 grams oftriethanolamine (TEA) were charged. 0.6 grams of Example 86 was chargedand the resulting product was maintained between 55-60° C. forapplication to urea.

Example 76

3.5 grams of tripropylene glycol mono methyl ether (TPM) and 12.93 gramsof dimethyl sulfoxide (DMSO) were heated to 45° C. under agitation. Next82.55 grams of N(n-butyl) thiophosphoric triamide (NBPT) powder was veryslowly charged initially allowing small portions to be solubilizedbefore adding more powder. Once the NBPT has been completelysolubilized, 0.6 grams of a scent package and 0.29 grams oftriethanolamine (TEA) were charged. 1.45 grams of Example 86 was chargedand the resulting product was maintained between 45-50° C. forapplication to urea.

Example 77

3.07 grams of tripropylene glycol mono methyl ether (TPM) and 23.82grams of dimethyl sulfoxide (DMSO) were heated to 40° C. underagitation. Next 72.23 grams of N(n-butyl) thiophosphoric triamide (NBPT)powder was slowly charged initially allowing small portions to besolubilized before adding more powder. Once the NBPT has been completelysolubilized, 0.53 grams of a scent package and 0.11 grams oftriethanolamine (TEA) were charged. 1.30 grams of Example 86 was chargedand the resulting product was maintained between 40-45° C. forapplication to urea.

Example 78

2.63 grams of tripropylene glycol mono methyl ether (TPM) and 34.70grams of dimethyl sulfoxide (DMSO) were heated to 40° C. underagitation. Next 61.91 grams of N(n-butyl) thiophosphoric triamide (NBPT)powder was slowly charged initially allowing small portions to besolubilized before adding more powder. Once the NBPT has been completelysolubilized, 0.45 grams of a scent package and 0.09 grams oftriethanolamine (TEA) were charged. 1.1 grams of Example 86 was chargedand the resulting product was maintained between 40-45° C. forapplication to urea.

Example 79

40 grams of dimethyl sulfoxide (DMSO) were heated to 45° C. underagitation. Next 60 grams of N(n-butyl) thiophosphoric triamide (NBPT)powder was slowly charged initially allowing small portions to besolubilized before adding more powder. Once the NBPT has been completelysolubilized, the solution was cooled to 38° C. and packaged.

Example 80

35 grams of dimethyl sulfoxide (DMSO) were heated to 45° C. underagitation. Next 65 grams of N(n-butyl) thiophosphoric triamide (NBPT)powder was slowly charged initially allowing small portions to besolubilized before adding more powder. Once the NBPT has been completelysolubilized, the solution was cooled to 38° C. and packaged.

Example 81

31.3 grams of dimethyl sulfoxide (DMSO) were heated to 45° C. underagitation. Next 20.6 grams of N(n-butyl) thiophosphoric triamide (NBPT)powder was slowly charged. Once the NBPT has been completelysolubilized, 45.6 grams of propylene glycol, 1.5 grams of scent, 0.5grams of triethanolamine, and 2.4 grams of Example 86 were charged,mixed for 15 minutes, cooled to 38° C. and packaged.

The chill points of some of the examples are listed below in Table 11wherein the various components are listed in grams (except for the chillpoint, which is in ° C.).

TABLE 11 Example Example Example Example Example Example Example 75 7677 78 79 80 81 TPM 1.44 3.50 3.07 2.63 NBPT 92.85 82.55 72.23 61.91 6065 20.6 DMSO 5.31 12.93 23.82 34.70 40 35 31.3 Scent 0.24 0.60 0.53 0.451.5 PG 45.6 Blue Dye 0.12 0.29 0.26 0.22 0.5 TEA 0.05 0.12 0.11 0.09 0.5CHILL POINT 56° C. 45° C. 21° C. −2° C. −13° C.< 4° C. −20° C.< * CHILLPOINT: temperature when example begins to cloud and loses liquidity. **TPM: tripropylene glycol mono methyl ether NBPT: N(n-butyl)thiophosphoric triamide DMSO: dimethyl sulfoxide PG: propylene glycolBlue dye: FD&C Blue #1 TEA: triethanolamine

Example 82

90 grams of propylene glycol were charged and placed under agitation.10.0 grams of Example 86 were charged, mixed for 15 minutes andpackaged.

Example 83

80 grams of propylene glycol were charged and placed under agitation.20.0 grams of Example 86 were charged, mixed for 15 minutes andpackaged.

Example 84

63 grams of propylene glycol were charged and placed under agitation. 30grams of Example 86 and 7 grams of DMSO were charged, mixed for 15minutes and packaged.

Example 85

56 grams of propylene glycol were charged and placed under agitation. 30grams of Example 86 and 14 grams of DMSO were charged, mixed for 15minutes and packaged.

Example 86

80 grams of DMSO were charged, placed under agitation, and heated to 60°C. 20 grams of a FD&C Blue #1 dye were charged, mixed for 2 hours coolto 38° C. and then packaged.

Example 86 is utilized as visual aid to confirm the evenness of thecoating of the surfaces of urea granules.

Example 87

9.85 grams of Example 52 were charged, placed under agitation and heatedto 40° C. 0.15 grams of Example 86 were charged, mixed for 15 minutes,cool to 38° C. and then packaged.

Example 88 Application of Examples to Urea Procedure for Coating UreaExamples

-   -   1. charging weight of urea as directed by Table 12 to a        container,    -   2. agitating slowly the urea was with overhead stirrer with U        shaped agitator blade,    -   3. setting the urea's temperature at 50° C.,    -   4. dripping slowly an example on the urea as directed by Table        12 while mixing in the amount,    -   5. increasing the agitation speed high enough, after the proper        weight of the example had been charged, to ensure even coating        of the urea by the example being tested,    -   6. pouring the coated urea into a jar and sealing it.

TABLE 12 Formulation for urease inhibitor coating of urea CompoundsWeight is in grams Urea 199.66 199.7 199.61 199.54 198.63 199.61 Example75 0.34 Example 76 0.3 Example 77 0.39 Example 78 0.46 Example 81 1.37Example 87 0.39 * Application ranges set to deliver 0.141% ureaseinhibitor to the surface of urea for all examples

The “coating quality rating” was based on a visual assessment ofcoverage of urea particles by utilizing the incorporated blue dye.Ratings were from 1-5 where 1=poor coverage showing large patches ofnon-blue particles versus 5=excellent coverage as determined by thecontinuity of the blue color and no non-blue patches.

The “packing flowability rating” was based on a visual assessment of:

-   -   1. Pouring 200 grams of coated urea particles into a quart jar        and capping with lid.    -   2. Sharply tapping the quart jar on a hard surface five times.    -   3. After 24 hours at room temperature, flip jar over. If        material remains in the jar's original bottom, a small spatula's        wooded handle is used to gently tap the jar's bottom.    -   4. Ratings were from 1-5 where 1=poor flowability where material        did not fall after 5 taps versus 5=excellent flowability where        all the material falls without a tap.

TABLE 13 Urease Formulation Coating Performance Coating Performance onUrea Coating rating: Flowability Rating: 1 = poor; 1 = lumps and poorflow; Example# 5 = full coating 5 = good flow (1 tap max) 75 5 5 76 5 577 5 4 78 5 4 81 5 3 87 5 4

Results show that the concentrated NBPT and a phosphinic acid organoamine/ammonium salt dissolved in a DMSO and another NOSDS caneffectively coat urea at moderate temperatures. Results of Example 81show while good coverage was achieved, the higher levels of NOSDSnegatively impacted the urea particles flowability, but it is stillacceptable.

Example 89

25.03 grams of Example 76 were charged to 174.98 grams of urea @50° C.using the setup of Example 88 resulting in about 10% NBPT applied to thesurfaces of urea. The example was extremely wet and possessed poor flowproperties.

Example 90

14.1 grams of Example 89 were charged to 85.9 grams of urea @50° C.using the setup of Example 88 resulting in about 0.141% NBPT applied tothe surfaces of all the urea. This example showed good coverage andpossessed good flow properties.

Example 91

14.1 grams of Example 89 were charged to 85.9 grams of urea @24° C.using the setup of Example 88 resulting in about 0.141% NBPT applied tothe surfaces of all the urea. This example required more mixing time todemonstrate fair coverage and to possess good flow properties.

Examples 89, 90, and 91 demonstrate that a high level of ureaseinhibitor can be applied to urea and then the coated urea can beutilized as a urease inhibitor carrier to be blended with untreatedurea. Example 90 demonstrates that a warmer urea requires less blendingtime.

Example 92 Crush Strength of Urease Inhibitor Coated Urea

Crush strength is the minimum pressure required to crush a granule ofurea. Crush strength is of concern during the application of urea and isa measure of the urea's expected broadcast distance. Crush strength isrelated to the maximum rotations per minute (rpm) for the spinnerportion of the urea spreader. The higher the rpms of the spinner, themore distance the urea can be broadcasted. High rpms require high crushstrength urea granules in order for the granules not to be pulverized todust by the broadcast process.

In order for the coated granules of urea to be tested, they were firstsifted through a series of screens to ensure that the urea granules tobe tested were of similar particle size as the urea particle size has animpact on crush resistance. A mesh size of 320-400 was chosen as theurea particle size. A New Leader crushing strength tester was usedutilizing a scale from 1-10 wherein a reading of 1 is rated very poorcrush strength. The results in Table 14 are for coated urea stored at25° C. and at 50° C. Also included in Table 14 is the weight percentageof DMSO of the composition of the coated urea.

TABLE 14 Crush Strength Performance on Urea Crush Strength CrushStrength % DMSO in stored 24 hrs. @ stored 24 hrs. @ Example# coatedurea 25 C. 50 C. 75 0.008% 7.0 7.55 76 0.0221% 7.7 7.30 77 0.0464% 7.357.70 78 0.0789% 7.85 7.40 81 0.2140% 4.9 5.70 Urea, std 0.0% 5.4 6.75 *Crush Strength numbers in Table 14 are the average of 10 individual runs

The results of the crush strength test were unexpected. The originalgoal of the invention was to be able to coat urea granules with higherlevels of NBPT without negatively impacting the urea granule's crushstrength. Unexpectedly, the low levels of DMSO (Examples 75-78) resultedin a urea granule with at least a 10% improvement in crush resistance.As expected, the higher level of DMSO in Example 81 and the high sampleloading on the surfaces of urea particles to achieve a 0.141% NBPTcoated urea lowered the crush resistance of the coated urea. Based onthe Table 14 data, the impact of the storage temperature on crushresistance did not demonstrate a strong trend for the coated urea (noteExamples 75, 76, 77, and 78). The uncoated urea and Example 81 showed asignificant loss of crush resistance stored at a lower temperature.

Example 94 Crush Strength of DMSO Coated Urea

The unexpected crush strength results of Example 93 led to an experimentwherein the urease inhibitor was removed and propylene glycol was chosenas the delivery solvent for DMSO to the surfaces of urea. Propyleneglycol was also chosen to examine whether it also had a role in the poorcrush resistance result of Example 81. Table 15 shows the formulationsto be utilized to coat urea

TABLE 15 Non-urease Formulations (in grams) Example Example ExampleExample Example Raw material 82 83 84 85 86 DMSO 8.0 16.00 31.00 38.0080 PG 90.0 80.00 63.00 56.00 Blue Dye 2.0 4.00 6.00 6.00 20 DMSO:dimethyl sulfoxide PG: propylene glycol Blue dye: FD&C Blue #1

The same procedure was utilized as in Example 88. Table 16 shows theformulations for the coated urea and the resulting performance of theevenness of the coated of the urea and the coated urea's flowability.

TABLE 16 Coated Urea Formulations Compounds Weight is in grams Urea199.66 199.66 199.66 199.66 199.91 Example 82 0.34 Example 83 0.34Example 84 0.34 Example 85 0.34 Example 86 0.09 Coverage 5 5 5 5 2rating: 1-5 1 = poor Flow 5 5 4 4 Did not Properties run rating: 1-5 1 =poor

Example 86 demonstrated poor coverage because it does not have a carriersolvent to assist in distributing the dye in DMSO onto the surfaces ofthe urea granules. However, it should be understood that a differentmethod of applying example 86 to the surfaces of the urea granules mightresult in better coverage (e.g., atomization onto the granules). Theprocedure for evaluating a coated urea particle's crush resistance wasthe same as utilized in Example 92. Table 17 has the crush strengthresults.

TABLE 17 Crush Strength Performance on Urea Crush Strength CrushStrength % DMSO in stored 24 hrs. @ stored 24 hrs. @ Example# coatedurea 25° C. 50° C. 82 0.0137% 7.00 7.55 83 0.0273% 7.65 8.00 84 0.0529%7.95 6.95 85 0.0648% 7.75 7.55 Urea, std 0.0% 5.4 6.75 * Crush Strengthnumbers in Table 17 are the average of 10 individual runs

The results of the crush strength test in Table 17 were similar to theresults in Table 14. Unexpectedly, the low levels of DMSO resulted in aurea granule with at least a 10% improvement in crush resistance. Thepresence of propylene glycol did not have an impact on the urea granulescrush strength. Based on the Table 17 data, the impact of the storagetemperature on crush resistance did not demonstrate a strong trend forthe coated urea Examples 82, 83, 84, and 85. This data verifies that thepresence of DMSO on and/or in urea granules at levels of <0.1% has apositive impact on the urea granules' crush strength. Table 14 and Table17 data also shows no decrease in crush strength of coated urea granulesuntil levels of DMSO are at 0.214% of the coated urea compositionsuggesting that levels of >0.2% DMSO would have minimal negative impacton coated urea granules' crush strength.

Example 95 Thermal Stability of NBPT

One of the advantages of this invention is the application, at moderatetemperatures, of thermally sensitive urease inhibitor onto the surfacesof urea. Moderate temperatures are defined as a range of about 20-70° C.Testing procedures were established to exactly weigh samples ofapproximately 1 gram of NBPT in an aluminum pan and expose them todifferent temperatures in an oven over varying amounts of time. Theinitial weight of NBPT in the pan was compared to the final weight ofsample in the pan. The % NBPT was then determined by HPLC of theresidual from the final weight pan by the following procedure:

1. Crush a portion of sample (˜5 g) using mortar and pestle.2. Weigh about a 100 mg sample, in duplicate, and add to separate 10 mLvolumetric flasks.3. Bring to volume of 10 ml volumetric flask with 50:50ACN(Acetonitrile):H₂O.4. Mix well by shaking.5. Transfer a portion through a Nylon 0.45 μm syringe filter into anHPLC vial.6. Inject on LC/UV (15-μg/mL calibration standard).

The results are listed for both tests in Table 18.

TABLE 18 NBPT Temperature Stability % Weight Sample-° C./ % NBPT presentby LC/UV Loss Time in sec % w/w Average Average NBPT-140° C./ 3.68%3.84% 13.42% 90 sec NBPT-140° C./ 3.99% 90 sec NBPT-120° C./ 4.79% 4.67%13.55% 180 sec NBPT-120° C./ 4.54% 180 sec NBPT-100° C./ 23.59% 22.9210.36% 300 sec NBPT-100° C./ 22.25% 300 sec NBPT-70° C./ 99.53% 99.380.26% 900 sec NBPT-70° C./ 99.23% 900 sec NBPT-50° C./ 99.17% 99.38 0.0%3600 sec NBPT-50° C./ 99.58% 3600 sec NBPT 99.35% 99.25 Not Applicablestd NBPT 99.16% std

HPLC results show that NBPT has poor thermal stability attemperatures >100° C. However, an examination of the weight loss versustemperature data shows that NBPT degrades but its degradation productdoes not disappear. Not to be bound by theory, it is thought that NBPTundergoes atmospheric thermal oxidation resulting in a degraded productthat contains sulfur and phosphorus (which are functionalities onun-degraded NBPT). HPLC data shows that exposure of NBPT to temperatures≥100° C. results in loss of the NBPT thereby resulting in a product thatcontains very little NBPT. Accordingly, any composition that is madeusing these higher temperatures result in a fertilizer product that isvastly inferior to the instant invention (which uses lowertemperatures).

For example, the HPLC data reveals that NBPT shows no degradation whenexposed for 15 minutes at a temperature of 70° C. The invention alsoshows that most application processes for coating urea with high NBPTactive compositions can be accomplished at temperatures of 50-60° C.

In an embodiment, the application of high NBPT active compositions tothe surfaces of urea is accomplished at processing temperatures thathave minimal impact on the purity of the NBPT. In a variation, theapplication of high NBPT active compositions to the surfaces of urea isaccomplished at processing temperatures that result in the formation ofa minimal amount of NBPT degradation products. In an embodiment, acomposition comprising a) urea and b) <0.2% DMSO results in a ureagranule with higher crush strength compared to the same urea with noDMSO.

In an embodiment, the composition of a liquid formulation comprises a)NOSDS and b) (hexylamino methylene, amino methylene) phosphinic acid,(C₈H₂₀N₂O₂P), and/or its salts wherein the NOSDS is comprised of one ormore solvents selected from the group consisting of aprotic organosolvents and protic organo solvents wherein one or more aprotic organosolvents are selected from the group consisting of:

-   -   a) dimethyl sulfoxide,    -   b) and one or more sulfoxide(s) selected from the group        consisting of dialkyl, diaryl, or alkylaryl sulfoxide(s)        selected from the formula structure:

R₉S(O)xR¹⁰

-   -   -   -   wherein            -   i) R⁹ and R¹⁰ are each independently a C₁-C₆ alkylene                group, an aryl group or C₁-C₃ alkylenearyl group,            -   ii) or R⁹ and R¹⁰ with the sulfur to which they are                attached form a 4 to 8 membered ring wherein R⁹ and R¹⁰                together are a C₁-C₆ alkylene group which optionally                contains one or more atoms selected from the group                consisting of O, S, Se, Te, N, and P in the ring,            -   iii) and x is 1 or 2,

    -   c) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate,

    -   d) one or more polyols capped with acetate or formate wherein        the polyol portion is selected from the group consisting of        ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol,        butylene glycol, trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol and sorbitan, glucose, fructose,        galactose and glycerin,

    -   e) one or more alkylene glycol alkyl ethers acetates selected        from the group consisting of dipropylene glycol methyl ether        acetate, tripropylene glycol methyl ether acetate, and        tripropylene glycol butyl ether acetate,

    -   f) one or more diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate,

    -   g) one or more alkyl pryrrolidone selected from the group        consisting of 1-Methyl-2-pyrrolidone and cyclohexylpyrrolidone,

    -   h) one or more members selected from the group consisting of        dimethylacetamide, dimethylformamide,        dimethyl-2-imidazolidinone, isophorone, hexamethylphosphoramide,        1,2-dimethyloxyethane, 2-methoxyethyl ether and limonene,

    -   i) one or more trialkyl phosphates selected from the group        consisting of triethyl phosphate and tributyl phosphate,        wherein said protic solvents are one or more members selected        from the group consisting of:

    -   a. one or more alcohols selected from the group consisting of        the family of C₁-C₁₀ alkanols,

    -   b. one or more polyols selected from the group consisting of        trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin,

    -   c. one or more polyalkylene glycols one or more members selected        from the group consisting of poly(C₁-C₁₀ alkylene) glycols,

    -   d. isopropylidene glycerol,

    -   e. one or more alkylene glycol alkyl of the formula:

-   -   wherein        -   i) R¹ is one or more members selected from the group            consisting of CH₃, C₂H₅, C₃H₇ and C₄H₉,        -   ii) R² is one or more members selected from the group            consisting of H and the formula structure:

-   -   -   -   wherein            -   (1) R⁴ is one or more members selected from the group                consisting of H and CH₃,            -   (2) and f is an integer between 1 and 15,

        -   iii) wherein R³ is one or more members selected from the            group consisting of H and CH₃,

    -   f. one or more alkyl lactates selected from the group consisting        of ethyl, propyl and butyl lactate,

    -   g. one or more alkanolamines selected from the group consisting        of alkanolamines of the structure:

-   -   -   wherein        -   iv) R⁵ is one or more members selected from the group            consisting of C₂H₄OR⁸ and C₃H₆OH,        -   v) R⁶ is: H, C₂H₄OR⁸ and C₃H₆OH,        -   vi) R⁷ is one or more members selected from the group            consisting of H, C₂H₄OR⁸ and C₃H₆OH,            -   wherein                -   (1) R⁸ is (C₂H₄O)_(g)H,                -    wherein g is an integer between 1-10,

    -   j) and glycerol carbonate,        and wherein said liquid formulation(s) have shown that they are

    -   extremely effective urease inhibitors,

    -   coat urea effectively,

    -   and coat DCD effectively.

In an embodiment, a method to make amino methylene phosphinic acids andor their salts comprises one or more steps comprising:

-   -   1) charging hypophosphorous acid/50% water. In a variation, the        water is displaced with an aprotic NOSDS. In a variation the        water is removed. In another variation, the water is removed        through the use of temperatures of 70-90° C. In another        variation, the water is removed through the use of temperatures        of 70-90° C. and by reducing the pressure of the reaction        vessel,    -   2) agitating the contents of the reaction vessel and charging        dimethyl sulfoxide and then paraformaldehyde while removing the        heat thereby generated by the reaction. In a variation, trioxane        is substituted for paraformaldehyde. In another variation, a        formaldehyde solution is substituted for paraformaldehyde. In        another variation, a mixture of one or more formaldehyde        variants is charged to the reactor vessel,    -   3) heating the composition to 50-80° C. and holding at 50-80° C.        until the composition clears,    -   4) cooling the temperature to 25-30° C. and then charging        hexylamine slowly while cooling on the reactor vessel in order        to maintain the temperature <40° C. In a variation, the reactor        vessel is not cooled. In another variation, the hexylamine is        charged slowly to the reaction vessel with no cooling,    -   5) after completing the hexylamine charge, the temperature is        raised to 50-70° C. and then held until composition's appearance        becomes clear,    -   6) charging sub-surface of ammonia gas,    -   7) continuing the NH₃ sparge at a temperature of 50-70° C. until        the composition's 10% pH reaches 6-10. In a variation, the 10%        pH reaches 7-9. In another variation, the pH reaches 7.5-8.5,    -   8) heating the composition to 80-100° C. while maintaining the        composition's 10% pH of 6-10. In a variation, the 10% pH is 7-9.        In another variation, the pH reaches 7.5-8.5 by adjusting the pH        through ammonia sparging,    -   9) holding at 80-100° C. for one hour while maintaining 10% pH        of 6-10. In a variation, maintaining 10% pH of 7-9. In another        variation, maintaining 10% pH of 7.5-8.5 pH through ammonia        sparging,    -   10) reducing the reaction vessel's pressure. In a variation, the        reaction vessel pressure is reduced through application of a        vacuum. In a variation, the reaction vessel pressure is reduced        to a pressure reading of ≤200 mm Hg. In a variation, the        reaction vessel pressure is reduced to a pressure reading of        ≤100 mm Hg. In a variation, the reaction vessel pressure is        reduced to a pressure reading of 60-100 mm Hg. In a variation,        the reaction vessel pressure is reduced to a pressure reading of        40-60 mm Hg. In a variation, the reaction vessel pressure is        reduced to a pressure reading of 20-40 mm Hg. In another        variation, the reaction vessel pressure is reduced to a pressure        reading of <20 mm Hg,    -   11) Vacuum is maintained until distillation ceases and %        moisture is less than 30%. In a variation, the % moisture is        less than 20%. In a variation, the % moisture is less than 10%.        In a variation, the % moisture is less than 5%. In another        variation, the moisture is less than 1%.

In an embodiment (aminomethylene)phosphinic acids andbis-(aminomethylene)phosphinic acids have improved urease inhibitionperformance. In a variation and not to be bound by theory,(aminomethylene)phosphinic acids and bis-(aminomethylene)phosphinicacids are more hydrolytically and thermally stable versus thetraditional phosphoric triamides.

In an embodiment, fertilizer compositions are comprised of a) one ormore members selected from the group consisting of(aminomethylene)phosphinic acids and bis-(aminomethylene)phosphinicacids, b) NOSDS, c) nitrogen sources wherein one or more nitrogensources are selected from the group consisting of: urea (molten/solid),manure, compost, urea formaldehyde reaction products (molten/solid),urea/ammonia/formaldehyde reaction products (molten/solid), ammoniumsulfate, anhydrous ammonia, urea/ammonium nitrate aqueous solutions(UAN) and other urea aqueous solutions.

In an embodiment, a method to make a fertilizer composition comprisesmaking a composition with a) one or more member selected from the groupconsisting of (aminomethylene)phosphinic acids andbis-(aminomethylene)phosphinic acids and b) molten urea.

In an embodiment, fertilizer compositions are comprised of a) one ormore member selected from the group consisting of(aminomethylene)phosphinic acids and bis-(aminomethylene)phosphinicacids, b) NOSDS, c) nitrogen sources and d) water wherein one or morenitrogen sources are selected from the group consisting of: urea(molten/solid), manure, compost, urea formaldehyde reaction products(molten/solid), urea/ammonia/formaldehyde reaction products(molten/solid), ammonium sulfate, anhydrous ammonia, urea/ammoniumnitrate aqueous solutions (UAN) and other urea aqueous solutions.

In an embodiment, the improved urease inhibition properties of(aminomethylene)phosphinic acids and bis-(aminomethylene)phosphinicacids applied as a coating on a nitrification inhibitor results in aflowable, dry powder for application to manure.

The following references are incorporated by reference in theirentireties for all purposes.

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It is contemplated and therefore within the scope of the presentinvention that any feature that is described above can be combined withany other feature that is described above. When mixtures, formulationsand/or compositions are discussed, it should be understood that thosemixtures, formulations and/or compositions are contemplated as beingparts of bigger mixtures, formulations and/or compositions includinghaving solvating agents. Moreover, it should be understood that thepresent invention contemplates minor modifications that can be made tothe compositions and methods of the present invention. In any event, thepresent invention is defined by the below claims.

What is claimed is:
 1. A solid fertilizer composition comprising: (a) aparticulate nitrogen source that comprises 83% to 99.99 wt % of thesolid fertilizer; and (b) a solid coating comprising N-(n-butyl)thiophosphoric triamide (NBPT) homogeneously coated on the nitrogensource, wherein: the NBPT in the solid coating ranging from 0.011 to 10wt % of the solid fertilizer and wherein said NBPT comprises 70-95 wt %of the solid coating.
 2. The solid fertilizer composition of claim 1,wherein the solid coating is initially applied on the particulatenitrogen source as a coating solution.
 3. The solid fertilizercomposition of claim 2, wherein the coating solution comprises NBPT anddimethyl sulfoxide (DMSO).
 4. The solid fertilizer composition of claim3, wherein DMSO ranges from 4% to 24% by weight in the coating solution.5. The solid fertilizer composition of claim 2, wherein the coatingsolution is applied at a temperature ranging from 20° C. to 70° C. 6.The solid fertilizer composition of claim 1, further comprising one ormore flow modifiers selected from the group consisting of silicas,hydrophobized silicas, soaps, inorganic powders, and nonionicsurfactants.
 7. The solid fertilizer composition of claim 6, wherein theone or more flow modifiers comprise 0.25 to 3.5 wt % of the solidfertilizer.
 8. The solid fertilizer composition of claim 1, wherein thesolid fertilizer composition further comprises a compositional weightpercent range of between about 0.005 to about 0.2% DMSO, and wherein theurease inhibitor coated urea has greater crush strength than an uncoatedparticulate nitrogen source.
 9. The solid fertilizer composition ofclaim 8, wherein the solid fertilizer composition comprises a crushstrength ranging from 7.0 to 7.85 when stored between 25° C. to 50° C.for 24 hours.
 10. The solid fertilizer composition of claim 9, whereinthe solid fertilizer composition comprises a percent increase in crushstrength ranging from about 8% to about 45% over the uncoatedparticulate nitrogen source when stored between 25° C. to 50° C. for 24hours.
 11. The solid fertilizer composition of claim 1, furthercomprising a colorant that indicates the coating homogeneity on theparticulate nitrogen source.
 12. The solid fertilizer composition ofclaim 11, wherein the colorant indicates depth penetration of the solidcoating into the particulate nitrogen source.
 13. A method of making thesolid fertilizer composition of claim 1 comprising: (a) providing theparticulate nitrogen source; (b) applying a coating solution comprisingN-(n-butyl) thiophosphoric triamide (NBPT) in a protic and/or aproticsolvent to the particulate nitrogen source; and (c) forming a solidcoating comprising N-(n-butyl) thiophosphoric triamide (NBPT) on thenitrogen source by subsequent drying and/or evaporation of the coatingsolution applied to the particulate nitrogen source of step (b) therebyforming the solid fertilizer composition.
 14. The method of claim 13,wherein the coating solution is applied to the particulate nitrogensource at a temperature ranging from 30° C. to 70° C.
 15. The method ofclaim 13, wherein the particulate nitrogen source is selected from thegroup consisting of: of a) urea, b) urea, formaldehyde reactionproducts, c) urea, formaldehyde, and ammonia reaction products, d)manure, e) dicyandiamide and f) compost.
 16. The method of claim 13,wherein step (b) comprises applying the coating solution to an outersurface of the particulate nitrogen source, wherein the particulatenitrogen source is at a temperature ranging from 30° C. to 70° C. andmixing the particulate nitrogen source having the coating solutionapplied thereon with at least one of a) mixers, b) blenders, and/or c)tumblers.
 17. The method of claim 13, wherein the solid fertilizercomposition is formed by a) rotating drum granulation, b) fluidized bedgranulation, or c) a prilling tower.
 18. The solid fertilizercomposition of claim 3, wherein the coating solution further comprisesadditional solvents selected from the group consisting of a) proticsolvents and b) aprotic solvents, wherein the protic solvents areselected from the group consisting of i) an alcohol from the family ofC₁₋₁₀ alkanols, ii) one or more polyols selected from the groupconsisting of trimethylol propane, trimethylol ethane, pentaerythritol,sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, iii)poly(C₁₋₁₀ alkylene) glycols, iv) one or more alkylene glycols selectedfrom the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2propylene glycol, and butylene glycol, v) isopropylidene glycerol vi)one or more alkylene glycol alkyl ethers represented by the structure

wherein R¹ is CH₃, C₂H₅, C₃H₇ or C₄H₉, R² is H or

R³ is H or CH₃, wherein R⁴ is H or CH₃, and f is an integer between 1and 15, vii) one or more alkyl lactates selected from the groupconsisting of ethyl lactate, propyl lactate and butyl lactate, viii) oneor more alkanolamines represented by the structure

wherein R⁵ is C₂H₄OR⁸ or C₃H₆OH, R⁶ is H, C₂H₄OR⁸ or C₃H₆OH, R⁷ is H,C₂H₄OR⁸ or C₃H₆OH, R⁸ is (C₂H₄O)_(g)H or H, and g is an integer between1 and 10, ix) and glycerol carbonate, and wherein the aprotic solventsare selected from the group consisting of i) dialkyl, diaryl, andalkylaryl sulfoxide(s) having the formulaR⁹S(O)xR¹⁰ wherein R⁹ and R¹⁰ are each independently a C₁₋₆ alkylenegroup, an aryl group, or C₁₋₃ alkylenearyl group or R⁹ and R¹⁰ with thesulfur to which they are attached form a 4 to 8 membered ring, whereinR⁹ and R¹⁰ together are a C₁₋₆ alkylene group which optionally containsone or more atoms selected from the group consisting of O, S, Se, Te, N,and P in the ring and x is 1 or 2, and wherein if R⁹ is C₁ then R¹⁰cannot be C₁, ii) one or more alkylene carbonates selected from thegroup consisting of ethylene carbonate, propylene carbonate and butylenecarbonate, iii) one or more polyols capped with acetate or formate,wherein the polyol portion selected from the group consisting ofethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butyleneglycol, trimethylol propane, trimethylol ethane, pentaerythritol,sorbitol, sorbitan, glucose, fructose, galactose and glycerin, iv) oneor more alkylene glycol alkyl ethers acetates selected from the groupconsisting of dipropylene glycol methyl ether acetate, tripropyleneglycol methyl ether acetate, and tripropylene glycol butyl etheracetate, v) isophorone, vi) one or more diesters selected from the groupconsisting of dimethylsuccinate, dimethyl adipate, diethyl glutarate,and dimethyl glutarate, vii) dimethylacetamide, viii) dimethylformamide,ix) dimethyl-2-imidazolidinone, x) one or more alkyl pyrrolidonesselected from the group consisting of 1-Methyl-2-pyrrolidone and butylpyrrolidone, xi) one or more organo phosphorous liquids selected fromthe group consisting of hexamethylphosphoramide and one or moretrialkylphosphates represented by the structure

wherein R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃ R₂₃ is alkyl radical —C₁H₃to —C₆H₁₃ R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃ xii)1,2-dimethyloxyethane, xiii) 2-methoxyethyl ether, xiv)cyclohexylpyrrolidone, and xv) limonene.
 19. The solid fertilizercomposition of claim 12, wherein the colorant does not comprise water oralcohol.
 20. The solid fertilizer composition of claim 1, wherein theparticular nitrogen source comprises a) urea, b) urea, formaldehydereaction products, c) urea, formaldehyde, and ammonia reaction products,d) manure, e) dicyandiamide, compost, and g) any combination thereof.